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In 2021 the International Science Programme (ISP) at Uppsala University celebrated its 60th anniversary. In spite of the Covid-19 pandemic, ISP made its best effort to honor the occasion and organised virtual workshops, meetings, and webinars during the year. This book represents the conclusive item of the jubilee year. Here we want to present the work ISP has performed since the beginning of the new millennium, narrated directly by the voices of scientists from all over the world who are or were part of the ISP family. They can now tell the significance and the impact that ISP has had on their own careers, their institutions and their countries. The book contains also contributions by the ISP staff, describing the historical evolution of ISP during the last 20 years, including for example the investment in gender equality which has raised a large interest in the supported partners. ISP has a long story, starting in 1961 as the International Seminar for Research and Education in Physics, when fellows from 14 developing countries were invited to Sweden to spend one year performing research work. Today the ISP core programme, which has evolved into three different programmes in physics, chemistry and mathematics, is devoted to assisting and strengthening research capacity building in a number of low and lower-middle income countries in Africa, Asia and Latin America. ISP supports both research groups and international scientific networks, with scientists from different countries. More recently, ISP has also been engaged as the Swedish coordinator of all Sida bilateral research programmes, as well as in other collaborations with for example Thailand International Cooperation Agency (TICA) and American Institute of Physics (AIP). The final aim of the book is to express not only the hard work performed by ISP staff and all the partners in the supported research groups and institutions, but especially the success of the efforts and the great enthusiasm that has permeated

In 2021 the International Science Programme (ISP) at Uppsala University celebrated its 60th anniversary. In spite of the Covid-19 pandemic, ISP made its best effort to honor the occasion and organised virtual workshops, meetings, and webinars during the year. This book represents the conclusive item of the jubilee year. Here we want to present the work ISP has performed since the beginning of the new millennium, narrated directly by the voices of scientists from all over the world who are or were part of the ISP family. They can now tell the significance and the impact that ISP has had on their own careers, their institutions and their countries. The book contains also contributions by the ISP staff, describing the historical evolution of ISP during the last 20 years, including for example the investment in gender equality which has raised a large interest in the supported partners. ISP has a long story, starting in 1961 as the International Seminar for Research and Education in Physics, when fellows from 14 developing countries were invited to Sweden to spend one year performing research work. Today the ISP core programme, which has evolved into three different programmes in physics, chemistry and mathematics, is devoted to assisting and strengthening research capacity building in a number of low and lower-middle income countries in Africa, Asia and Latin America. ISP supports both research groups and international scientific networks, with scientists from different countries. More recently, ISP has also been engaged as the Swedish coordinator of all Sida bilateral research programmes, as well as in other collaborations with for example Thailand International Cooperation Agency (TICA) and American Institute of Physics (AIP). The final aim of the book is to express not only the hard work performed by ISP staff and all the partners in the supported research groups and institutions, but especially the success of the efforts and the great enthusiasm that has permeated

In 2021 the International Science Programme (ISP) at Uppsala University celebrated its 60th anniversary. In spite of the Covid-19 pandemic, ISP made its best effort to honor the occasion and organised virtual workshops, meetings, and webinars during the year. This book represents the conclusive item of the jubilee year. Here we want to present the work ISP has performed since the beginning of the new millennium, narrated directly by the voices of scientists from all over the world who are or were part of the ISP family. They can now tell the significance and the impact that ISP has had on their own careers, their institutions and their countries. The book contains also contributions by the ISP staff, describing the historical evolution of ISP during the last 20 years, including for example the investment in gender equality which has raised a large interest in the supported partners. ISP has a long story, starting in 1961 as the International Seminar for Research and Education in Physics, when fellows from 14 developing countries were invited to Sweden to spend one year performing research work. Today the ISP core programme, which has evolved into three different programmes in physics, chemistry and mathematics, is devoted to assisting and strengthening research capacity building in a number of low and lower-middle income countries in Africa, Asia and Latin America. ISP supports both research groups and international scientific networks, with scientists from different countries. More recently, ISP has also been engaged as the Swedish coordinator of all Sida bilateral research programmes, as well as in other collaborations with for example Thailand International Cooperation Agency (TICA) and American Institute of Physics (AIP). The final aim of the book is to express not only the hard work performed by ISP staff and all the partners in the supported research groups and institutions, but especially the success of the efforts and the great enthusiasm that has permeated

In 2021 the International Science Programme (ISP) at Uppsala University celebrated its 60th anniversary. In spite of the Covid-19 pandemic, ISP made its best effort to honor the occasion and organised virtual workshops, meetings, and webinars during the year. This book represents the conclusive item of the jubilee year. Here we want to present the work ISP has performed since the beginning of the new millennium, narrated directly by the voices of scientists from all over the world who are or were part of the ISP family. They can now tell the significance and the impact that ISP has had on their own careers, their institutions and their countries. The book contains also contributions by the ISP staff, describing the historical evolution of ISP during the last 20 years, including for example the investment in gender equality which has raised a large interest in the supported partners. ISP has a long story, starting in 1961 as the International Seminar for Research and Education in Physics, when fellows from 14 developing countries were invited to Sweden to spend one year performing research work. Today the ISP core programme, which has evolved into three different programmes in physics, chemistry and mathematics, is devoted to assisting and strengthening research capacity building in a number of low and lower-middle income countries in Africa, Asia and Latin America. ISP supports both research groups and international scientific networks, with scientists from different countries. More recently, ISP has also been engaged as the Swedish coordinator of all Sida bilateral research programmes, as well as in other collaborations with for example Thailand International Cooperation Agency (TICA) and American Institute of Physics (AIP). The final aim of the book is to express not only the hard work performed by ISP staff and all the partners in the supported research groups and institutions, but especially the success of the efforts and the great enthusiasm that has permeated

In 2021 the International Science Programme (ISP) at Uppsala University celebrated its 60th anniversary. In spite of the Covid-19 pandemic, ISP made its best effort to honor the occasion and organised virtual workshops, meetings, and webinars during the year. This book represents the conclusive item of the jubilee year. Here we want to present the work ISP has performed since the beginning of the new millennium, narrated directly by the voices of scientists from all over the world who are or were part of the ISP family. They can now tell the significance and the impact that ISP has had on their own careers, their institutions and their countries. The book contains also contributions by the ISP staff, describing the historical evolution of ISP during the last 20 years, including for example the investment in gender equality which has raised a large interest in the supported partners. ISP has a long story, starting in 1961 as the International Seminar for Research and Education in Physics, when fellows from 14 developing countries were invited to Sweden to spend one year performing research work. Today the ISP core programme, which has evolved into three different programmes in physics, chemistry and mathematics, is devoted to assisting and strengthening research capacity building in a number of low and lower-middle income countries in Africa, Asia and Latin America. ISP supports both research groups and international scientific networks, with scientists from different countries. More recently, ISP has also been engaged as the Swedish coordinator of all Sida bilateral research programmes, as well as in other collaborations with for example Thailand International Cooperation Agency (TICA) and American Institute of Physics (AIP). The final aim of the book is to express not only the hard work performed by ISP staff and all the partners in the supported research groups and institutions, but especially the success of the efforts and the great enthusiasm that has permeated

We performed a spectroscopic study on the m-MTDATA (donor) and PPT (acceptor) molecular vertical heterostructure. The electronic properties of the donor/acceptor interface have been comprehensively characterized by synchrotron radiation-based photoelectron spectroscopy and near-edge x-ray absorption fine structure. The spectroscopic results reveal the existence of new hybridization states in the original molecular energy gap, likely attributed to the interaction between the donor and the acceptor molecules at the interface. Such hybridized states can have a significant impact on the charge transport in organic electronic devices based on donor-acceptor molecules and can explain the increased efficiency of device using such molecules.

We demonstrate site-specific X-ray induced fragmentation across the sulfur L-edge of protonated cystine, the dimer of the amino acid cysteine. Ion yield NEXAFS were performed in the gas phase using electrospray ionization (ESI) in combination with an ion trap. The interpretation of the sulfur Ledge NEXAFS spectrum is supported by Restricted Open-Shell Configuration Interaction (ROCIS) calculations. The fragmentation pathway of triply charged cystine ions was modeled by Molecular Dynamics (MD) simulations. We have deduced a possible pathway of fragmentation upon excitation and ionization of S 2p electrons. The disulfide bridge breaks for resonant excitation at lower photon energies but remains intact upon higher energy resonant excitation and upon ionization of S 2p. The larger fragments initially formed subsequently break into smaller fragments.

The starburst pi-conjugated molecule based on triphenylamine (TPA) building blocks, 4,4',4 ''-tris(N-3-ethylphenyl-N-phenylamino)triphenylamine (C57H48N4, m-MTDATA), is widely used in optoelectronic devices due to its electron-donating properties. The electronic structure of m-MTDATA adsorbed on an Au(111) surface was investigated by means of photoelectron spectroscopy (PES) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. The results were further compared to gas-hase measurements and DFT calculations. Our results clearly indicate a significant molecule-substrate interaction that induces considerable modifications on the electronic structure of the adsorbate compared to the isolated molecule. The energy level alignment analysis shows that the HOMO-LUMO gap is filled by new interface states.

In this article, we analyze the electronic structure modifications of triphenylamine (TPA), a well-known electron donor molecule widely used in photovoltaics and optoelectronics, upon deposition on Au(111) at a monolayer coverage. A detailed study was carried out by synchrotron radiation-based photoelectron spectroscopy, near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, scanning tunneling microscopy (STM), and ab initio calculations. We detect a new feature in the pre-edge energy region of the N K-edge NEXAFS spectrum that extends over 3 eV, which we assign to transitions involving new electronic states. According to our calculations, upon adsorption, a number of new unoccupied electronic states fill the energy region between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the free TPA molecule and give rise to the new feature the pre-edge region of the NEXAFS spectrum. This finding highlights the occurrence of a considerable modification of the electronic structure of TPA. The appearance of new states in the HOMO-LUMO gap of TPA when adsorbed on Au(111) has crucial implications for the design of molecular nanoelectronic devices based on similar donor systems.

We demonstrate site-specific X-ray induced fragmentation across the sulfur L-edge of protonated cystine, the dimer of the amino acid cysteine. Ion yield NEXAFS were performed in the gas phase using electrospray ionization (ESI) in combination with an ion trap. The interpretation of the sulfur Ledge NEXAFS spectrum is supported by Restricted Open-Shell Configuration Interaction (ROCIS) calculations. The fragmentation pathway of triply charged cystine ions was modeled by Molecular Dynamics (MD) simulations. We have deduced a possible pathway of fragmentation upon excitation and ionization of S 2p electrons. The disulfide bridge breaks for resonant excitation at lower photon energies but remains intact upon higher energy resonant excitation and upon ionization of S 2p. The larger fragments initially formed subsequently break into smaller fragments.

In this article, we analyze the electronic structure modifications of triphenylamine (TPA), a well-known electron donor molecule widely used in photovoltaics and optoelectronics, upon deposition on Au(111) at a monolayer coverage. A detailed study was carried out by synchrotron radiation-based photoelectron spectroscopy, near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, scanning tunneling microscopy (STM), and ab initio calculations. We detect a new feature in the pre-edge energy region of the N K-edge NEXAFS spectrum that extends over 3 eV, which we assign to transitions involving new electronic states. According to our calculations, upon adsorption, a number of new unoccupied electronic states fill the energy region between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the free TPA molecule and give rise to the new feature the pre-edge region of the NEXAFS spectrum. This finding highlights the occurrence of a considerable modification of the electronic structure of TPA. The appearance of new states in the HOMO-LUMO gap of TPA when adsorbed on Au(111) has crucial implications for the design of molecular nanoelectronic devices based on similar donor systems.

In this article, we analyze the electronic structure modifications of triphenylamine (TPA), a well-known electron donor molecule widely used in photovoltaics and optoelectronics, upon deposition on Au(111) at a monolayer coverage. A detailed study was carried out by synchrotron radiation-based photoelectron spectroscopy, near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, scanning tunneling microscopy (STM), and ab initio calculations. We detect a new feature in the pre-edge energy region of the N K-edge NEXAFS spectrum that extends over 3 eV, which we assign to transitions involving new electronic states. According to our calculations, upon adsorption, a number of new unoccupied electronic states fill the energy region between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the free TPA molecule and give rise to the new feature the pre-edge region of the NEXAFS spectrum. This finding highlights the occurrence of a considerable modification of the electronic structure of TPA. The appearance of new states in the HOMO-LUMO gap of TPA when adsorbed on Au(111) has crucial implications for the design of molecular nanoelectronic devices based on similar donor systems., QC 20220404

The starburst pi-conjugated molecule based on triphenylamine (TPA) building blocks, 4,4',4 ''-tris(N-3-ethylphenyl-N-phenylamino)triphenylamine (C57H48N4, m-MTDATA), is widely used in optoelectronic devices due to its electron-donating properties. The electronic structure of m-MTDATA adsorbed on an Au(111) surface was investigated by means of photoelectron spectroscopy (PES) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. The results were further compared to gas-hase measurements and DFT calculations. Our results clearly indicate a significant molecule-substrate interaction that induces considerable modifications on the electronic structure of the adsorbate compared to the isolated molecule. The energy level alignment analysis shows that the HOMO-LUMO gap is filled by new interface states., QC 20220325

We performed a spectroscopic study on the m-MTDATA (donor) and PPT (acceptor) molecular vertical heterostructure. The electronic properties of the donor/acceptor interface have been comprehensively characterized by synchrotron radiation-based photoelectron spectroscopy and near-edge x-ray absorption fine structure. The spectroscopic results reveal the existence of new hybridization states in the original molecular energy gap, likely attributed to the interaction between the donor and the acceptor molecules at the interface. Such hybridized states can have a significant impact on the charge transport in organic electronic devices based on donor-acceptor molecules and can explain the increased efficiency of device using such molecules., QC 20220411

We demonstrate site-specific X-ray induced fragmentation across the sulfur L-edge of protonated cystine, the dimer of the amino acid cysteine. Ion yield NEXAFS were performed in the gas phase using electrospray ionization (ESI) in combination with an ion trap. The interpretation of the sulfur Ledge NEXAFS spectrum is supported by Restricted Open-Shell Configuration Interaction (ROCIS) calculations. The fragmentation pathway of triply charged cystine ions was modeled by Molecular Dynamics (MD) simulations. We have deduced a possible pathway of fragmentation upon excitation and ionization of S 2p electrons. The disulfide bridge breaks for resonant excitation at lower photon energies but remains intact upon higher energy resonant excitation and upon ionization of S 2p. The larger fragments initially formed subsequently break into smaller fragments.

In this article, we analyze the electronic structure modifications of triphenylamine (TPA), a well-known electron donor molecule widely used in photovoltaics and optoelectronics, upon deposition on Au(111) at a monolayer coverage. A detailed study was carried out by synchrotron radiation-based photoelectron spectroscopy, near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, scanning tunneling microscopy (STM), and ab initio calculations. We detect a new feature in the pre-edge energy region of the N K-edge NEXAFS spectrum that extends over 3 eV, which we assign to transitions involving new electronic states. According to our calculations, upon adsorption, a number of new unoccupied electronic states fill the energy region between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the free TPA molecule and give rise to the new feature the pre-edge region of the NEXAFS spectrum. This finding highlights the occurrence of a considerable modification of the electronic structure of TPA. The appearance of new states in the HOMO-LUMO gap of TPA when adsorbed on Au(111) has crucial implications for the design of molecular nanoelectronic devices based on similar donor systems.

This joint experimental-theoretical spectroscopy study of the fullerene derivative PC60BM ([6,6]-phenyl-C-60-butyric acid methyl ester) aims to improve the understanding of the effect of photooxidation on its electronic structure. We have studied spin-coated thin films of PC60BM by X-ray Photoelectron Spectroscopy (XPS), Near-edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy, and Fourier Transform Infrared Spectroscopy (FTIR), before and after intentional exposure to simulated sunlight in air for different lengths of time. The pi* resonance in the C1s NEXAFS spectrum was found to be a very sensitive probe for the early changes to the fullerene cage, while FTIR spectra, in combination with O1s NEXAFS spectra, enabled the identification of the oxidation products. The changes observed in the spectra obtained by these complementary methods were compared with the corresponding Density Functional Theory (DFT) calculated single-molecule spectra of a large set of in silico generated oxidation products of PC60BM where oxygen atoms were attached to the C-60 cage. This comparison confirms that photooxidation of PC60BM disrupts the conjugation of the fullerene cage by a transition from sp(2) to sp(3)-hybridized carbon and causes the formation of several oxidation products, earlier proposed for C-60. The agreement between experimental and calculated IR spectra suggests moreover the presence of dicarbonyl and anhydride structures on the fullerene cage, in combination with cage opening at the adsorption site. By including PC60BM with physisorbed O-2 molecules on the cage in our theoretical description in order to model oxygen diffused through the film, the experimental O1s XPS and O1s NEXAFS spectra could be reproduced.

This joint experimental-theoretical spectroscopy study of the fullerene derivative PC60BM ([6,6]-phenyl-C-60-butyric acid methyl ester) aims to improve the understanding of the effect of photooxidation on its electronic structure. We have studied spin-coated thin films of PC60BM by X-ray Photoelectron Spectroscopy (XPS), Near-edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy, and Fourier Transform Infrared Spectroscopy (FTIR), before and after intentional exposure to simulated sunlight in air for different lengths of time. The pi* resonance in the C1s NEXAFS spectrum was found to be a very sensitive probe for the early changes to the fullerene cage, while FTIR spectra, in combination with O1s NEXAFS spectra, enabled the identification of the oxidation products. The changes observed in the spectra obtained by these complementary methods were compared with the corresponding Density Functional Theory (DFT) calculated single-molecule spectra of a large set of in silico generated oxidation products of PC60BM where oxygen atoms were attached to the C-60 cage. This comparison confirms that photooxidation of PC60BM disrupts the conjugation of the fullerene cage by a transition from sp(2) to sp(3)-hybridized carbon and causes the formation of several oxidation products, earlier proposed for C-60. The agreement between experimental and calculated IR spectra suggests moreover the presence of dicarbonyl and anhydride structures on the fullerene cage, in combination with cage opening at the adsorption site. By including PC60BM with physisorbed O-2 molecules on the cage in our theoretical description in order to model oxygen diffused through the film, the experimental O1s XPS and O1s NEXAFS spectra could be reproduced.

This joint experimental-theoretical spectroscopy study of the fullerene derivative PC60BM ([6,6]-phenyl-C-60-butyric acid methyl ester) aims to improve the understanding of the effect of photooxidation on its electronic structure. We have studied spin-coated thin films of PC60BM by X-ray Photoelectron Spectroscopy (XPS), Near-edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy, and Fourier Transform Infrared Spectroscopy (FTIR), before and after intentional exposure to simulated sunlight in air for different lengths of time. The pi* resonance in the C1s NEXAFS spectrum was found to be a very sensitive probe for the early changes to the fullerene cage, while FTIR spectra, in combination with O1s NEXAFS spectra, enabled the identification of the oxidation products. The changes observed in the spectra obtained by these complementary methods were compared with the corresponding Density Functional Theory (DFT) calculated single-molecule spectra of a large set of in silico generated oxidation products of PC60BM where oxygen atoms were attached to the C-60 cage. This comparison confirms that photooxidation of PC60BM disrupts the conjugation of the fullerene cage by a transition from sp(2) to sp(3)-hybridized carbon and causes the formation of several oxidation products, earlier proposed for C-60. The agreement between experimental and calculated IR spectra suggests moreover the presence of dicarbonyl and anhydride structures on the fullerene cage, in combination with cage opening at the adsorption site. By including PC60BM with physisorbed O-2 molecules on the cage in our theoretical description in order to model oxygen diffused through the film, the experimental O1s XPS and O1s NEXAFS spectra could be reproduced.

This joint experimental-theoretical spectroscopy study of the fullerene derivative PC60BM ([6,6]-phenyl-C-60-butyric acid methyl ester) aims to improve the understanding of the effect of photooxidation on its electronic structure. We have studied spin-coated thin films of PC60BM by X-ray Photoelectron Spectroscopy (XPS), Near-edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy, and Fourier Transform Infrared Spectroscopy (FTIR), before and after intentional exposure to simulated sunlight in air for different lengths of time. The pi* resonance in the C1s NEXAFS spectrum was found to be a very sensitive probe for the early changes to the fullerene cage, while FTIR spectra, in combination with O1s NEXAFS spectra, enabled the identification of the oxidation products. The changes observed in the spectra obtained by these complementary methods were compared with the corresponding Density Functional Theory (DFT) calculated single-molecule spectra of a large set of in silico generated oxidation products of PC60BM where oxygen atoms were attached to the C-60 cage. This comparison confirms that photooxidation of PC60BM disrupts the conjugation of the fullerene cage by a transition from sp(2) to sp(3)-hybridized carbon and causes the formation of several oxidation products, earlier proposed for C-60. The agreement between experimental and calculated IR spectra suggests moreover the presence of dicarbonyl and anhydride structures on the fullerene cage, in combination with cage opening at the adsorption site. By including PC60BM with physisorbed O-2 molecules on the cage in our theoretical description in order to model oxygen diffused through the film, the experimental O1s XPS and O1s NEXAFS spectra could be reproduced.

We demonstrate site-specific X-ray induced fragmentation across the sulfur L-edge of protonated cystine, the dimer of the amino acid cysteine. Ion yield NEXAFS were performed in the gas phase using electrospray ionization (ESI) in combination with an ion trap. The interpretation of the sulfur Ledge NEXAFS spectrum is supported by Restricted Open-Shell Configuration Interaction (ROCIS) calculations. The fragmentation pathway of triply charged cystine ions was modeled by Molecular Dynamics (MD) simulations. We have deduced a possible pathway of fragmentation upon excitation and ionization of S 2p electrons. The disulfide bridge breaks for resonant excitation at lower photon energies but remains intact upon higher energy resonant excitation and upon ionization of S 2p. The larger fragments initially formed subsequently break into smaller fragments.

In this article, we analyze the electronic structure modifications of triphenylamine (TPA), a well-known electron donor molecule widely used in photovoltaics and optoelectronics, upon deposition on Au(111) at a monolayer coverage. A detailed study was carried out by synchrotron radiation-based photoelectron spectroscopy, near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, scanning tunneling microscopy (STM), and ab initio calculations. We detect a new feature in the pre-edge energy region of the N K-edge NEXAFS spectrum that extends over 3 eV, which we assign to transitions involving new electronic states. According to our calculations, upon adsorption, a number of new unoccupied electronic states fill the energy region between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the free TPA molecule and give rise to the new feature the pre-edge region of the NEXAFS spectrum. This finding highlights the occurrence of a considerable modification of the electronic structure of TPA. The appearance of new states in the HOMO-LUMO gap of TPA when adsorbed on Au(111) has crucial implications for the design of molecular nanoelectronic devices based on similar donor systems.

This joint experimental-theoretical spectroscopy study of the fullerene derivative PC60BM ([6,6]-phenyl-C-60-butyric acid methyl ester) aims to improve the understanding of the effect of photooxidation on its electronic structure. We have studied spin-coated thin films of PC60BM by X-ray Photoelectron Spectroscopy (XPS), Near-edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy, and Fourier Transform Infrared Spectroscopy (FTIR), before and after intentional exposure to simulated sunlight in air for different lengths of time. The pi* resonance in the C1s NEXAFS spectrum was found to be a very sensitive probe for the early changes to the fullerene cage, while FTIR spectra, in combination with O1s NEXAFS spectra, enabled the identification of the oxidation products. The changes observed in the spectra obtained by these complementary methods were compared with the corresponding Density Functional Theory (DFT) calculated single-molecule spectra of a large set of in silico generated oxidation products of PC60BM where oxygen atoms were attached to the C-60 cage. This comparison confirms that photooxidation of PC60BM disrupts the conjugation of the fullerene cage by a transition from sp(2) to sp(3)-hybridized carbon and causes the formation of several oxidation products, earlier proposed for C-60. The agreement between experimental and calculated IR spectra suggests moreover the presence of dicarbonyl and anhydride structures on the fullerene cage, in combination with cage opening at the adsorption site. By including PC60BM with physisorbed O-2 molecules on the cage in our theoretical description in order to model oxygen diffused through the film, the experimental O1s XPS and O1s NEXAFS spectra could be reproduced.

We demonstrate site-specific X-ray induced fragmentation across the sulfur L-edge of protonated cystine, the dimer of the amino acid cysteine. Ion yield NEXAFS were performed in the gas phase using electrospray ionization (ESI) in combination with an ion trap. The interpretation of the sulfur Ledge NEXAFS spectrum is supported by Restricted Open-Shell Configuration Interaction (ROCIS) calculations. The fragmentation pathway of triply charged cystine ions was modeled by Molecular Dynamics (MD) simulations. We have deduced a possible pathway of fragmentation upon excitation and ionization of S 2p electrons. The disulfide bridge breaks for resonant excitation at lower photon energies but remains intact upon higher energy resonant excitation and upon ionization of S 2p. The larger fragments initially formed subsequently break into smaller fragments.

In this article, we analyze the electronic structure modifications of triphenylamine (TPA), a well-known electron donor molecule widely used in photovoltaics and optoelectronics, upon deposition on Au(111) at a monolayer coverage. A detailed study was carried out by synchrotron radiation-based photoelectron spectroscopy, near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, scanning tunneling microscopy (STM), and ab initio calculations. We detect a new feature in the pre-edge energy region of the N K-edge NEXAFS spectrum that extends over 3 eV, which we assign to transitions involving new electronic states. According to our calculations, upon adsorption, a number of new unoccupied electronic states fill the energy region between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the free TPA molecule and give rise to the new feature the pre-edge region of the NEXAFS spectrum. This finding highlights the occurrence of a considerable modification of the electronic structure of TPA. The appearance of new states in the HOMO-LUMO gap of TPA when adsorbed on Au(111) has crucial implications for the design of molecular nanoelectronic devices based on similar donor systems.

We present an ab initio density functional theory study of the magnetic properties of manganese phthalocyanine dimers, where we focus on the magnetic coupling between the Mn centers and on how it is affected by external factors like chemisorption or atomic axial ligands. We have studied several different configurations for the gas phase dimers, which resulted in ferromagnetic couplings of different magnitudes. For the bare dimer we find a significant ferromagnetic coupling between the Mn centers, which decreases by about 20% when a H atom is adsorbed on one of the Mn atoms and is reduced to about 7% when a Cl atom is adsorbed. The magnetic coupling is almost fully quenched when the dimer, bare or with the H ligand, is deposited on the ferromagnetic substrate Co(001). Our calculations indicate that the coupling between the two Mn atoms principally occurs via a superexchange interaction along two possible paths within a Mn-N-Mn-N four-atom loop. When these electrons get involved in chemical bonding outside the dimer itself, an appreciable alteration of the overlap between Mn and N molecular orbitals along the loop occurs, and consequently, the magnetic interaction between the Mn centers varies. We show that this is reflected by the electronic structure of the dimer in various configurations and is also visible in the structure of the atomic loop. The chemical tuning of the magnetic coupling is highly relevant for the design of nanodevices like molecular spin valves, where the molecules need to be anchored to a support.

We present an ab initio density functional theory study of the magnetic properties of manganese phthalocyanine dimers, where we focus on the magnetic coupling between the Mn centers and on how it is affected by external factors like chemisorption or atomic axial ligands. We have studied several different configurations for the gas phase dimers, which resulted in ferromagnetic couplings of different magnitudes. For the bare dimer we find a significant ferromagnetic coupling between the Mn centers, which decreases by about 20% when a H atom is adsorbed on one of the Mn atoms and is reduced to about 7% when a Cl atom is adsorbed. The magnetic coupling is almost fully quenched when the dimer, bare or with the H ligand, is deposited on the ferromagnetic substrate Co(001). Our calculations indicate that the coupling between the two Mn atoms principally occurs via a superexchange interaction along two possible paths within a Mn-N-Mn-N four-atom loop. When these electrons get involved in chemical bonding outside the dimer itself, an appreciable alteration of the overlap between Mn and N molecular orbitals along the loop occurs, and consequently, the magnetic interaction between the Mn centers varies. We show that this is reflected by the electronic structure of the dimer in various configurations and is also visible in the structure of the atomic loop. The chemical tuning of the magnetic coupling is highly relevant for the design of nanodevices like molecular spin valves, where the molecules need to be anchored to a support.

We present an ab initio density functional theory study of the magnetic properties of manganese phthalocyanine dimers, where we focus on the magnetic coupling between the Mn centers and on how it is affected by external factors like chemisorption or atomic axial ligands. We have studied several different configurations for the gas phase dimers, which resulted in ferromagnetic couplings of different magnitudes. For the bare dimer we find a significant ferromagnetic coupling between the Mn centers, which decreases by about 20% when a H atom is adsorbed on one of the Mn atoms and is reduced to about 7% when a Cl atom is adsorbed. The magnetic coupling is almost fully quenched when the dimer, bare or with the H ligand, is deposited on the ferromagnetic substrate Co(001). Our calculations indicate that the coupling between the two Mn atoms principally occurs via a superexchange interaction along two possible paths within a Mn-N-Mn-N four-atom loop. When these electrons get involved in chemical bonding outside the dimer itself, an appreciable alteration of the overlap between Mn and N molecular orbitals along the loop occurs, and consequently, the magnetic interaction between the Mn centers varies. We show that this is reflected by the electronic structure of the dimer in various configurations and is also visible in the structure of the atomic loop. The chemical tuning of the magnetic coupling is highly relevant for the design of nanodevices like molecular spin valves, where the molecules need to be anchored to a support.

Recent experiments have highlighted the efficiency of nonprecious metal-based hybrid structures, such as g-C3N4/MoS2 and g-C3N4/graphene for hydrogen evolution reaction (HER). This work focuses on the interface effects of such hybrid heterostructures that could lead to the enhanced catalytic activity of g-C3N4. We have concentrated on the hybrid electrocatalysts with the architecture g-C3N4/X (X = WTe2, MoS2, and graphene), where the interface plays an important role in the overall HER. These promising candidates have been assessed using three main factors extracted from density functional theory calculations, namely: (i) the free energy of hydrogen adsorption on the catalytic site ΔGH, (ii) Schottky barrier potentials, and (iii) induced charge polarization across the interface. We have found that particularly g-C3N4/WTe2 displays a suitable combination of the investigated properties standing out as a potential electrocatalyst for efficient hydrogen evolution reaction. Furthermore, the electronic structure fingerprints controlling the HER thermodynamics have been investigated. In particular, the N–H bonds have been found to display strong s–p hybridization and, additionally, ΔGH decreases as the center of N p-band approaches the Fermi energy. This is also a relevant result in understanding HER mechanisms of organic compounds.

With recent advances in the areas of nanostructure fabrication and molecular spintronics the idea of using single molecule magnets as building blocks for the next generation electronic devices becomes viable. A particular example represents a metal-organic complex in which organic ligands surround a rare-earth element or transition metal. Recently, it was explicitly shown that the relative position of the ligands with respect to each other can be reversibly changed by the external voltage without any need of the chemical modification of the sample. This opens a way of the electrical tuning of the Kondo effect in such metal-organic complexes. In this work, we present a detailed and systematic analysis of this effect in TbPc2 from an ab initio perspective and compare the obtained results with the existing experimental data.

Recent experiments have highlighted the efficiency of nonprecious metal-based hybrid structures, such as g-C3N4/MoS2 and g-C3N4/graphene for hydrogen evolution reaction (HER). This work focuses on the interface effects of such hybrid heterostructures that could lead to the enhanced catalytic activity of g-C3N4. We have concentrated on the hybrid electrocatalysts with the architecture g-C3N4/X (X = WTe2, MoS2, and graphene), where the interface plays an important role in the overall HER. These promising candidates have been assessed using three main factors extracted from density functional theory calculations, namely: (i) the free energy of hydrogen adsorption on the catalytic site ΔGH, (ii) Schottky barrier potentials, and (iii) induced charge polarization across the interface. We have found that particularly g-C3N4/WTe2 displays a suitable combination of the investigated properties standing out as a potential electrocatalyst for efficient hydrogen evolution reaction. Furthermore, the electronic structure fingerprints controlling the HER thermodynamics have been investigated. In particular, the N–H bonds have been found to display strong s–p hybridization and, additionally, ΔGH decreases as the center of N p-band approaches the Fermi energy. This is also a relevant result in understanding HER mechanisms of organic compounds.

We present an ab initio density functional theory study of the magnetic properties of manganese phthalocyanine dimers, where we focus on the magnetic coupling between the Mn centers and on how it is affected by external factors like chemisorption or atomic axial ligands. We have studied several different configurations for the gas phase dimers, which resulted in ferromagnetic couplings of different magnitudes. For the bare dimer we find a significant ferromagnetic coupling between the Mn centers, which decreases by about 20% when a H atom is adsorbed on one of the Mn atoms and is reduced to about 7% when a Cl atom is adsorbed. The magnetic coupling is almost fully quenched when the dimer, bare or with the H ligand, is deposited on the ferromagnetic substrate Co(001). Our calculations indicate that the coupling between the two Mn atoms principally occurs via a superexchange interaction along two possible paths within a Mn-N-Mn-N four-atom loop. When these electrons get involved in chemical bonding outside the dimer itself, an appreciable alteration of the overlap between Mn and N molecular orbitals along the loop occurs, and consequently, the magnetic interaction between the Mn centers varies. We show that this is reflected by the electronic structure of the dimer in various configurations and is also visible in the structure of the atomic loop. The chemical tuning of the magnetic coupling is highly relevant for the design of nanodevices like molecular spin valves, where the molecules need to be anchored to a support.

We present an ab initio density functional theory study of the magnetic properties of manganese phthalocyanine dimers, where we focus on the magnetic coupling between the Mn centers and on how it is affected by external factors like chemisorption or atomic axial ligands. We have studied several different configurations for the gas phase dimers, which resulted in ferromagnetic couplings of different magnitudes. For the bare dimer we find a significant ferromagnetic coupling between the Mn centers, which decreases by about 20% when a H atom is adsorbed on one of the Mn atoms and is reduced to about 7% when a Cl atom is adsorbed. The magnetic coupling is almost fully quenched when the dimer, bare or with the H ligand, is deposited on the ferromagnetic substrate Co(001). Our calculations indicate that the coupling between the two Mn atoms principally occurs via a superexchange interaction along two possible paths within a Mn-N-Mn-N four-atom loop. When these electrons get involved in chemical bonding outside the dimer itself, an appreciable alteration of the overlap between Mn and N molecular orbitals along the loop occurs, and consequently, the magnetic interaction between the Mn centers varies. We show that this is reflected by the electronic structure of the dimer in various configurations and is also visible in the structure of the atomic loop. The chemical tuning of the magnetic coupling is highly relevant for the design of nanodevices like molecular spin valves, where the molecules need to be anchored to a support.

With recent advances in the areas of nanostructure fabrication and molecular spintronics the idea of using single molecule magnets as building blocks for the next generation electronic devices becomes viable. A particular example represents a metal-organic complex in which organic ligands surround a rare-earth element or transition metal. Recently, it was explicitly shown that the relative position of the ligands with respect to each other can be reversibly changed by the external voltage without any need of the chemical modification of the sample. This opens a way of the electrical tuning of the Kondo effect in such metal-organic complexes. In this work, we present a detailed and systematic analysis of this effect in TbPc2 from an ab initio perspective and compare the obtained results with the existing experimental data., Funding Agencies:Russian Science Foundation (RSF) 18-72-00058Russian Foundation for Basic Research (RFBR) 20-52-S52001

Recent advances in operando-synchrotron-based X-ray techniques are making it possible to address fundamental questions related to complex proton-coupled electron transfer reactions, for instance, the electrocatalytic water splitting process. However, it is still a grand challenge to assess the ability of the different techniques to characterize the relevant intermediates, with minimal interference on the reaction mechanism. To this end, we have developed a novel methodology employing X-ray photoelectron spectroscopy (XPS) in connection with the liquid-jet approach to probe the electrochemical properties of a model electrocatalyst, [RuII(bpy)2(py)-(OH2)]2+, in an aqueous environment. There is a unique fingerprint of the extremely important higher-valence ruthenium−oxo species in the XPS spectra along the oxidation reaction pathway. Furthermore, a sequential method combining quantum mechanics and molecular mechanics is used to illuminate the underlying physical chemistry of such systems. This study provides the basis for the future development of in-operando XPS techniques for water oxidation reactions.

Using the MoS2-WTe2 heterostructure as a model system combined with electrochemical microreactors and density function theory calculations, it is shown that heterostructured contacts enhance the hydrogen evolution reaction (HER) activity of monolayer MoS2. Two possible mechanisms are suggested to explain this enhancement: efficient charge injection through large-area heterojunctions between MoS2 and WTe2 and effective screening of mirror charges due to the semimetallic nature of WTe2. The dielectric screening effect is proven minor, probed by measuring the HER activity of monolayer MoS2 on various support substrates with dielectric constants ranging from 4 to 300. Thus, the enhanced HER is attributed to the increased charge injection into MoS2 through large-area heterojunctions. Based on this understanding, a MoS2/WTe2 hybrid catalyst is fabricated with an HER overpotential of -140 mV at 10 mA cm(-2), a Tafel slope of 40 mV dec(-1), and long stability. These results demonstrate the importance of interfacial design in transition metal dichalcogenide HER catalysts. The microreactor platform presents an unambiguous approach to probe interfacial effects in various electrocatalytic reactions.

Unveiling the interplay of semiconducting organic molecules with their environment, such as inorganic materials or atmospheric gas, is the first step to designing hybrid devices with tailored optical, electronic or magnetic properties. The present article focuses on a double-decker lutetium phthalocyanine known as an intrinsic semiconducting molecule, holding a Lu ion in its center, sandwiched between two phthalocyanine rings. Carrying out experimental investigations by means of electron spectroscopies, X-ray diffraction and scanning probe microscopies together with advanced ab initio computations, allows us to unveil how this molecule interacts with weakly or highly reactive surfaces. Our studies reveal that a molecule-surface interaction is evidenced when molecules arc deposited on bare silicon or on gold surfaces together with a charge transferred from the substrate to the molecule, affecting to a higher extent the lower ring of the molecule. A new packing of the molecules on gold surfaces is proposed: an eclipse configuration in which molecules are flat and parallel to the surface, even for thick films of several hundreds of nanometers. Surprisingly, a robust tolerance of the double-decker phthalocyanine toward oxygen molecules is demonstrated, leading to weak chemisorption of oxygen below 100 K.

The starburst pi-conjugated molecule 4,4 ',4 ''-tris(N-3-methylphenyl-N-phenyl-amino)triphenylamine (C57H48N4, m-MTDATA), based on triphenylamine (TPA) building blocks, is widely used in optoelectronic devices due to its good electron-donor characteristics. The electronic structure of m-MTDATA was investigated for the first time in the gas phase by means of PhotoElectron Spectroscopy (PES) and Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy. The combination of Density Functional Theory (DFT) calculations with the experimental spectra provides a comprehensive description of the molecular electronic structure. Moreover, by comparing the results with previous TPA measurements, we could shed light on how the electronic structure evolves when the molecular size is increased. We found that the C 1s photoelectron spectra of m-MTDATA and TPA are similar, due to the balance of the counter-acting effects of the electronegativity of the N atoms and the delocalization of the amine lone-pair electrons. In contrast, the increased number of N atoms (i.e. N lone pairs) in m-MTDATA determines a three-peak feature in the outermost valence binding energy region with strong contributions by the N 2p(z) orbitals. We also obtained a decrease of the HOMO-LUMO gap for m-MTDATA, which points to improved electron donating properties of m-MTDATA with respect to TPA.

It is established that density functional theory (DFT) + U is a better choice compared to DFT for describing the correlated electron metal center in organometallics. The value of the Hubbard U parameter may be determined from linear response, either by considering the response of the metal site alone or by additionally considering the response of other sites in the compound. We analyze here in detail the influence of ligand shells of increasing size on the U parameter calculated from the linear response for five transition metal phthalocyanines. We show that the calculated multiple-site U is larger than the single-site U by as much as 1 eV and the ligand atoms that are mainly responsible for this difference are the isoindole nitrogen atoms directly bonded to the central metal atom. This suggests that a different U value may be required for computations of chemisorbed molecules compared to physisorbed and gas-phase cases.

It is established that density functional theory (DFT) + U is a better choice compared to DFT for describing the correlated electron metal center in organometallics. The value of the Hubbard U parameter may be determined from linear response, either by considering the response of the metal site alone or by additionally considering the response of other sites in the compound. We analyze here in detail the influence of ligand shells of increasing size on the U parameter calculated from the linear response for five transition metal phthalocyanines. We show that the calculated multiple-site U ligand atoms that are mainly responsible for this difference are is larger than the single-site U by as much as 1 eV and the ligand atoms that are mainly responsible for this difference are the isoindole nitrogen atoms directly bonded to the central metal atom. This suggests that a different U value may be required for computations of chemisorbed molecules compared to physisorbed and gas-phase cases., QC 20190516

Recent advances in operando-synchrotron-based X-ray techniques are making it possible to address fundamental questions related to complex proton-coupled electron transfer reactions, for instance, the electrocatalytic water splitting process. However, it is still a grand challenge to assess the ability of the different techniques to characterize the relevant intermediates, with minimal interference on the reaction mechanism. To this end, we have developed a novel methodology employing X-ray photoelectron spectroscopy (XPS) in connection with the liquid-jet approach to probe the electrochemical properties of a model electrocatalyst, [RuII(bpy)2(py)(OH2)]2+, in an aqueous environment. There is a unique fingerprint of the extremely important higher-valence ruthenium–oxo species in the XPS spectra along the oxidation reaction pathway. Furthermore, a sequential method combining quantum mechanics and molecular mechanics is used to illuminate the underlying physical chemistry of such systems. This study provides the basis for the future development of in-operando XPS techniques for water oxidation reactions.

Using the MoS2-WTe2 heterostructure as a model system combined with electrochemical microreactors and density function theory calculations, it is shown that heterostructured contacts enhance the hydrogen evolution reaction (HER) activity of monolayer MoS2. Two possible mechanisms are suggested to explain this enhancement: efficient charge injection through large-area heterojunctions between MoS2 and WTe2 and effective screening of mirror charges due to the semimetallic nature of WTe2. The dielectric screening effect is proven minor, probed by measuring the HER activity of monolayer MoS2 on various support substrates with dielectric constants ranging from 4 to 300. Thus, the enhanced HER is attributed to the increased charge injection into MoS2 through large-area heterojunctions. Based on this understanding, a MoS2/WTe2 hybrid catalyst is fabricated with an HER overpotential of −140 mV at 10 mA cm−2, a Tafel slope of 40 mV dec−1, and long stability. These results demonstrate the importance of interfacial design in transition metal dichalcogenide HER catalysts. The microreactor platform presents an unambiguous approach to probe interfacial effects in various electrocatalytic reactions.

Recent advances in operando-synchrotron-based X-ray techniques are making it possible to address fundamental questions related to complex proton-coupled electron transfer reactions, for instance, the electrocatalytic water splitting process. However, it is still a grand challenge to assess the ability of the different techniques to characterize the relevant intermediates, with minimal interference on the reaction mechanism. To this end, we have developed a novel methodology employing X-ray photoelectron spectroscopy (XPS) in connection with the liquid-jet approach to probe the electrochemical properties of a model electrocatalyst, [RuII(bpy)2(py)-(OH2)]2+, in an aqueous environment. There is a unique fingerprint of the extremely important higher-valence ruthenium−oxo species in the XPS spectra along the oxidation reaction pathway. Furthermore, a sequential method combining quantum mechanics and molecular mechanics is used to illuminate the underlying physical chemistry of such systems. This study provides the basis for the future development of in-operando XPS techniques for water oxidation reactions.

Using the MoS2-WTe2 heterostructure as a model system combined with electrochemical microreactors and density function theory calculations, it is shown that heterostructured contacts enhance the hydrogen evolution reaction (HER) activity of monolayer MoS2. Two possible mechanisms are suggested to explain this enhancement: efficient charge injection through large-area heterojunctions between MoS2 and WTe2 and effective screening of mirror charges due to the semimetallic nature of WTe2. The dielectric screening effect is proven minor, probed by measuring the HER activity of monolayer MoS2 on various support substrates with dielectric constants ranging from 4 to 300. Thus, the enhanced HER is attributed to the increased charge injection into MoS2 through large-area heterojunctions. Based on this understanding, a MoS2/WTe2 hybrid catalyst is fabricated with an HER overpotential of -140 mV at 10 mA cm(-2), a Tafel slope of 40 mV dec(-1), and long stability. These results demonstrate the importance of interfacial design in transition metal dichalcogenide HER catalysts. The microreactor platform presents an unambiguous approach to probe interfacial effects in various electrocatalytic reactions.

For the electrochemical hydrogen evolution reaction (HER), the electrical properties of catalysts can play an important role in influencing the overall catalytic activity. This is particularly important for semiconducting HER catalysts such as MoS2, which has been extensively studied over the last decade. Herein, on-chip microreactors on two model catalysts, semiconducting MoS2 and semimetallic WTe2, are employed to extract the effects of individual factors and study their relations with the HER catalytic activity. It is shown that electron injection at the catalyst/current collector interface and intralayer and interlayer charge transport within the catalyst can be more important than thermodynamic energy considerations. For WTe2, the site-dependent activities and the relations of the pure thermodynamics to the overall activity are measured and established, as the microreactors allow precise measurements of the type and area of the catalytic sites. The approach presents opportunities to study electrochemical reactions systematically to help establish rational design principles for future electrocatalysts.