33 results on '"Gap-Sue Kim"'
Search Results
2. ExoMol line lists – XLVI. Empirical rovibronic spectra of silicon mononitrate (SiN) covering the six lowest electronic states and four isotopologues
- Author
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Mikhail Semenov, Nicholas Clark, Sergei N Yurchenko, Gap-Sue Kim, and Jonathan Tennyson
- Subjects
Space and Planetary Science ,Astronomy and Astrophysics - Abstract
Silicon mononitride (28Si14N, 29Si14N, 30Si14N, 28Si15N) line lists covering infrared, visible, and ultraviolet regions are presented. The SiNful line lists produced by ExoMol include rovibronic transitions between six electronic states: $X\, {}^{2}\Sigma ^{+}$, $A\, {}^{2}\Pi$, $B\, {}^{2}\Sigma ^{+}$, $D\, {}^{2}\Delta$, $a\, {}^{4}\Sigma ^{+}$, $b\, {}^{4}\Pi$. The ab initio potential energy and coupling curves, computed at the multireference configuration interaction (MRCI/aug-cc-pVQZ) level of theory, are refined for the observed states by fitting their analytical representations to 1052 experimentally derived SiN energy levels determined from rovibronic bands belonging to the X–X, A–X, and B–X electronic systems through the MARVEL procedure. The SiNful line lists are compared to previously observed spectra, recorded and calculated lifetimes, and previously calculated partition functions. SiNful is available via the www.exomol.com database.
- Published
- 2022
3. AB INITIO STUDY OF THE EXCITED STATES OF O2
- Author
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Gap-Sue Kim, Sergei Yurchenko, and Wilfrid Somogyi
- Published
- 2022
4. ROVIBRONIC INFRARED AND VISIBLE LINE LIST FOR O2
- Author
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Wilfrid Somogyi, Gap-Sue Kim, and Sergei Yurchenko
- Published
- 2022
5. HIGH LEVEL AB INITIO STUDY OF THE ROVIBRONIC SPECTRUM OF SULFUR MONOXIDE (SO): DIABATIC REPRESENTATION
- Author
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Ryan Brady, Jonathan Tennyson, Sergei Yurchenko, Wilfrid Somogyi, and Gap-Sue Kim
- Published
- 2022
6. AN EXOMOL LINE LIST FOR SO: ROVIBRONIC SPECTRUM OF SULFUR MONOXIDE
- Author
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Wilfrid Somogyi, Sergei N. Yurchenko, Ryan Brady, Gap-Sue Kim, and Jonathan Tennyson
- Subjects
Line list ,chemistry.chemical_compound ,Materials science ,Sulfur monoxide ,chemistry ,Analytical chemistry ,Spectrum (topology) - Published
- 2021
7. AN AB INITIO STUDY OF ELECTRONICALLY EXCITED STATES OF SiN AND SO
- Author
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Nicholas Clark, Wilfrid Somogyi, Gap-Sue Kim, Sergei N. Yurchenko, Ryan Brady, and Mikhail Semenov
- Subjects
Physics ,Excited state ,Ab initio ,Atomic physics - Published
- 2021
8. The reaction of the tricarbon with acetylene: An ab initio/RRKM study of the potential energy surface and product branching ratios
- Author
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Mebel, Alexander M., Gap-Sue Kim, Kislov, Vadim V., and Kaiser, Ralf I.
- Subjects
Acetylene -- Chemical properties ,Potential energy -- Research ,Chemicals, plastics and rubber industries - Abstract
An initio calculations of the potential energy surface for the reaction of the tricarbon with acetylene were performed at the RCCSD(T)/cc-pVQZ/B3LYP/6-311G(d,p)+ZPE[B3LYP/6-311G(d,p) level. The results show that this reaction starts from the formation of the 30(didehydrovinylidene)cyclopropene intermediate i1 or the five-member ring structure i7.
- Published
- 2007
9. Gas-Phase Synthesis of the Elusive Cyclooctatetraenyl Radical (C8 H7 ) via Triplet Aromatic Cyclooctatetraene (C8 H8 ) and Non-Aromatic Cyclooctatriene (C8 H8 ) Intermediates
- Author
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Michael Lucas, Ralf I. Kaiser, Gap-Sue Kim, Alexander M. Mebel, Aaron M. Thomas, and Long Zhao
- Subjects
010405 organic chemistry ,Chemistry ,Radical ,chemistry.chemical_element ,General Chemistry ,Reaction intermediate ,010402 general chemistry ,Photochemistry ,01 natural sciences ,Catalysis ,0104 chemical sciences ,Gas phase ,Cyclooctatetraene ,chemistry.chemical_compound ,Reaction dynamics ,Carbon - Abstract
The 1,2,4,7-cyclooctatetraenyl radical (C8H7) has been synthesized for the very first time via the bimolecular gas-phase reaction of ground-state carbon atoms with 1,3,5-cycloheptatriene (C7H8) on the triplet surface under single-collision conditions. The barrier-less route to the cyclic 1,2,4,7-cyclooctatetraenyl radical accesses exotic reaction intermediates on the triplet surface, which cannot be synthesized via classical organic chemistry methods: the triplet non-aromatic 2,4,6-cyclooctatriene (C8H8) and the triplet aromatic 1,3,5,7-cyclooctatetraene (C8H8). Our approach provides a clean gas-phase synthesis of this hitherto elusive cyclic radical species 1,2,4,7-cyclooctatetraenyl via a single-collision event and opens up a versatile, unconventional path to access this previously largely obscure class of cyclooctatetraenyl radicals, which have been impossible to access through classical synthetic methods.
- Published
- 2017
10. Gas‐Phase Synthesis of the Elusive Cyclooctatetraenyl Radical (C 8 H 7 ) via Triplet Aromatic Cyclooctatetraene (C 8 H 8 ) and Non‐Aromatic Cyclooctatriene (C 8 H 8 ) Intermediates
- Author
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Michael Lucas, Aaron M. Thomas, Long Zhao, Ralf I. Kaiser, Gap‐Sue Kim, and Alexander M. Mebel
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010304 chemical physics ,0103 physical sciences ,General Medicine ,010402 general chemistry ,01 natural sciences ,0104 chemical sciences - Published
- 2017
11. Anab initioStudy of Excited States of C4H3Radical
- Author
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Gap-Sue Kim and Joong Chul Choe
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Astrochemistry ,Field (physics) ,Chemistry ,Radical ,Ab initio ,General Chemistry ,Configuration interaction ,010402 general chemistry ,01 natural sciences ,0104 chemical sciences ,Excited state ,0103 physical sciences ,Complete active space ,Atomic physics ,010303 astronomy & astrophysics ,Basis set - Abstract
Carbon-rich radicals are important for understanding chemistry of flames as well as astrochemistry. However, they are elusive for both experiments and computations, due to the peculiarity of radicals. Here, we calculated excited states of the 1-buten-3-yn-2-yl (HCCCCH2 , i-C4H3 ) and n-C4H3 (HCCCHCH) radicals with the state-of-the-art complete active space self-consistent field (CASSCF) and multi-reference configuration interaction (MRCI) methods using the 6-311 + G(3df,2p) and aTVZ basis sets. The vertical energies for the seven excited states of each of the two isomers were obtained with the MRCI method at the geometries optimized at the CASSCF/6-311G(d,p) level. The result using the aTVZ basis set has been more reliable than predicted with the 6-311 + G(3df,2p) basis set with the relative stability of the ground states of the two isomers better predicted in comparison to existing data. We believe that our results will be useful for understanding the chemistry of carbon-rich radicals.
- Published
- 2016
12. Dynamic Stark-Induced Coherent π-Electron Rotations in a Chiral Aromatic Ring Molecule: Application to Phenylalanine
- Author
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Hirobumi Mineo, Sheng Hsien Lin, Gap Sue Kim, and Yuichi Fujimura
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Angular momentum ,010304 chemical physics ,Chemistry ,Degenerate energy levels ,Electron ,010402 general chemistry ,01 natural sciences ,0104 chemical sciences ,Coherent ring ,Schrödinger equation ,symbols.namesake ,Coherent control ,Position (vector) ,Quantum mechanics ,Excited state ,0103 physical sciences ,symbols ,Physical and Theoretical Chemistry - Abstract
We present the results of a theoretical study on dynamic Stark-induced coherent π-electron rotations in a chiral aromatic ring molecule. This is an extension of our previous papers, which have been published in Mineo , H. [ Phys. Chem. Chem. Phys. 2016 , 18 , 26786 - 26795 ] and Mineo , H. [ J. Phys. Chem. Lett. 2018 , 9 , 5521 - 5526 ]. In those papers, the time-dependent Schrodinger equation was solved under a restricted condition in which a degenerate excited state should be formed at the center of the two relevant excited states by dynamic Stark effects. The dynamic Stark-induced degenerate state (DSIDS) is essential to create unidirectional π-electron rotations. In the present theoretical treatment, the above restriction is relaxed and the DSIDS is set to be at any energy position between the two excited states. This indicates a wide applicability of the dynamic Stark effects to coherent control of photophysical properties in aromatic molecules, such as coherent ring currents and current-induced magnetic fluxes of low-symmetric aromatic molecules. Analytical expressions for the coherent π-electron angular momentum are derived within a three-electronic-state model by using the Laplace transform method. The validity of the developed theoretical procedure is demonstrated by carrying out simulations of the coherent angular momentum of l-phenylalanine. Effects of varying the DSIDS on the time-dependent coherent angular momentum and the populations in the three electronic states are examined, and the results are analyzed using approximate expressions for the time-dependent coherent angular momentum and the populations. Modulations in the time-dependent coherent angular momentum appear when the DSIDS is set at an energy position between the two excited states, while there are no beating modulations when the DSIDS is set at the center position. Such differences originate from whether interferences between the two dressed states take place or not.
- Published
- 2019
13. Quantum Design for Ultrafast Probing of Molecular Chirality through Enantiomer-Specific Coherent π-Electron Angular Momentum
- Author
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Hirobumi Mineo, Sheng Hsien Lin, Yuichi Fujimura, and Gap Sue Kim
- Subjects
Angular momentum ,Circular dichroism ,Degenerate energy levels ,Electron ,010402 general chemistry ,01 natural sciences ,Molecular physics ,0104 chemical sciences ,Magnetic field ,Excited state ,0103 physical sciences ,General Materials Science ,Physical and Theoretical Chemistry ,010306 general physics ,Chirality (chemistry) ,Magnetic dipole - Abstract
Probing molecular chirality, right-handed or left-handed chiral molecules, is one of the central issues in chemistry and biochemistry. The conventional theory of optical activity measurements such as circular dichroism has been derived in the second-order processes involving electric and magnetic dipole moments, and the signals are very weak. We propose an efficient enantiomer-probing scenario for chiral aromatic ring molecules based on photoinduced coherent π-electron rotations. In our model, the resultant laser-induced currents themselves produce a strong magnetic field. The principle for probing molecular chirality is a utilization of dynamic Stark effects of two electronic excited states. These electronic states subjected to strong nonresonant linearly polarized UV lasers become degenerate to create enantiomer-specific electronic angular momentum. A pair of enantiomers of phenylalanine was taken as an example. Enantiomer-specific coherent magnetic fluxes on the order of a few teslas can be generated in several tens of femtoseconds. The direct detection of strong coherent magnetic fluxes could be carried out by time-resolved magnetic force microscopy experiments. The results provide important implications for the measurement of effective probing of chiral aromatic molecules.
- Published
- 2018
14. Induction of unidirectional π-electron rotations in low-symmetry aromatic ring molecules using two linearly polarized stationary lasers
- Author
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Hirobumi Mineo, Sheng Hsien Lin, Yoshiaki Teranishi, Masahiro Yamaki, Gap-Sue Kim, and Yuichi Fujimura
- Subjects
Physics ,Angular momentum ,010304 chemical physics ,Degenerate energy levels ,General Physics and Astronomy ,Expectation value ,010402 general chemistry ,01 natural sciences ,0104 chemical sciences ,Schrödinger equation ,symbols.namesake ,Quantum mechanics ,Excited state ,0103 physical sciences ,symbols ,Rotating wave approximation ,Physical and Theoretical Chemistry ,Atomic physics ,Angular momentum operator ,Ground state - Abstract
A new laser-control scenario of unidirectional π-electron rotations in a low-symmetry aromatic ring molecule having no degenerate excited states is proposed. This scenario is based on dynamic Stark shifts of two relevant excited states using two linearly polarized stationary lasers. Each laser is set to selectively interact with one of the two electronic states, the lower and higher excited states are shifted up and down with the same rate, respectively, and the two excited states become degenerate at their midpoint. One of the four control parameters of the two lasers, i.e. two frequencies and two intensities, determines the values of all the other parameters. The direction of π-electron rotations, clockwise or counter-clockwise rotation, depends on the sign of the relative phase of the two lasers at the initial time. An analytical expression for the time-dependent expectation value of the rotational angular momentum operator is derived using the rotating wave approximation (RWA). The control scenario depends on the initial condition of the electronic states. The control scenario with the ground state as the initial condition was applied to toluene molecules. The derived time-dependent angular momentum consists of a train of unidirectional angular momentum pulses. The validity of the RWA was checked by numerically solving the time-dependent Schrödinger equation. The simulation results suggest an experimental realization of the induction of unidirectional π-electron rotations in low-symmetry aromatic ring molecules without using any intricate quantum-optimal control procedure. This may open up an effective generation method of ring currents and current-induced magnetic fields in biomolecules such as amino acids having aromatic ring molecules for searching their interactions.
- Published
- 2016
15. On the validity of the independent interaction model for generation of dynamic Stark-induced degenerate states in chiral aromatic ring molecules
- Author
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Gap-Sue Kim, Sheng Hsien Lin, Yuichi Fujimura, and Hirobumi Mineo
- Subjects
Physics ,Angular momentum ,Linear polarization ,Degenerate energy levels ,General Physics and Astronomy ,Interaction model ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Laser ,01 natural sciences ,0104 chemical sciences ,law.invention ,law ,Excited state ,Molecule ,Physical and Theoretical Chemistry ,Atomic physics ,0210 nano-technology ,Chirality (chemistry) - Abstract
Dynamic Stark-induced degenerate state (DSIDS) is essential to generate electronic coherent angular momentum to identify molecular chirality. We previously derived DSIDS for phenylalanine enantiomers in the independent interaction model (IIM), in which two linearly polarized nonresonant UV lasers independently interact with relevant two electronic excited states. We present a numerical method to derive DSIDS beyond IIM. Here, both lasers interact with both excited states, and laser input parameters are determined for DSIDS located at the center of the excited states. The numerical results reasonably agree with those calculated in the IIM, which elucidate the validity of DSIDS in the IIM.
- Published
- 2020
16. Oxidation of the para-Tolyl Radical by Molecular Oxygen under Single-Collison Conditions: Formation of the para-Toloxy Radical
- Author
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Gap-Sue Kim, Aaron M. Thomas, Beni B. Dangi, Ralf I. Kaiser, Alexander M. Mebel, and Tao Yang
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010304 chemical physics ,Radical ,010402 general chemistry ,Photochemistry ,01 natural sciences ,0104 chemical sciences ,Reaction rate ,Crossed molecular beam ,chemistry.chemical_compound ,chemistry ,Reaction dynamics ,0103 physical sciences ,Thermochemistry ,Atomic oxygen ,General Materials Science ,Molecular oxygen ,Physical and Theoretical Chemistry ,Methyl group - Abstract
Crossed molecular beam experiments were performed to elucidate the chemical dynamics of the para-tolyl (CH3C6H4) radical reaction with molecular oxygen (O2) at an average collision energy of 35.3 ± 1.4 kJ mol–1. Combined with theoretical calculations, the results show that para-tolyl is efficiently oxidized by molecular oxygen to para-toloxy (CH3C6H4O) plus ground-state atomic oxygen via a complex forming, overall exoergic reaction (experimental, −33 ± 16 kJ mol–1; computational, −42 ± 8 kJ mol–1). The reaction dynamics are analogous to those observed for the phenyl (C6H5) plus molecular oxygen system which suggests the methyl group is a spectator during para-tolyl oxidation and that application of phenyl thermochemistry and reaction rates to para-substituted aryls is likely a suitable approximation.
- Published
- 2016
17. Understanding of cholesterol-binding protein structure with molecular dynamics
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Hyejin Yoon, Soonmin Jang, Hyung Ho Lee, Eun Sook Joo, Gap-Sue Kim, and Se Won Suh
- Subjects
Inorganic Chemistry ,Molecular dynamics ,Structural Biology ,Chemistry ,Biophysics ,Cholesterol-binding protein ,General Materials Science ,Physical and Theoretical Chemistry ,Condensed Matter Physics ,Biochemistry - Published
- 2017
18. The reaction of phenyl radical with molecular oxygen: A G2M study of the potential energy surface
- Author
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Tokmakov, Igor V., Gap-Sue Kim, Kislov, Vadim V., Mebel, Alexander M., and Ming C. Lin
- Subjects
Potential energy -- Research ,Radicals (Chemistry) -- Research ,Chemical reactions -- Research ,Chemicals, plastics and rubber industries - Abstract
The potential energy surface for the reaction of C6H5 with O2 is investigated by performing Ab initio GM calculations. However, since C6H5O + O and C5H5 + CO2 are expected to be the major primary products of the C6H5 + O2 reaction and thermal decomposition of C6H5O leads to C5H5 + C, cyclopentadienyl radical are likely to be the major product of phenyl radical oxidation.
- Published
- 2005
19. Theoretical investigations of spectroscopy and excited state dynamics of adenine
- Author
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Michitoshi Hayashi, Alexander M. Mebel, Kuo Kan Liang, K.Y. Baek, S. H. Lin, Gap-Sue Kim, and Chih-Hao Chin
- Subjects
Resonance fluorescence ,Chemistry ,Excited state ,Dynamics (mechanics) ,Strong coupling ,General Physics and Astronomy ,Harmonic potential ,State (functional analysis) ,Physical and Theoretical Chemistry ,Atomic physics ,Spectroscopy ,Spectral line - Abstract
A set of harmonic potential surfaces have been obtained at the CASSCF/6-311+G** level for the ground, n–p*, and p–p* states of 9Hadenine. They have been used to analyze experimental R2PI and resonance fluorescence spectra and the excited state lifetimes of adenine. A tentative plausible assignment has been proposed, which takes into account a strong coupling between these electronic states. Using the potential surfaces, the excess energy dependence of the excited state lifetimes of adenine has been interpreted, and the lifetime of the n–p * state at the band origin has also been estimated to be in the order of 10 ns.
- Published
- 2007
20. The Reaction of Tricarbon with Acetylene: An Ab Initio/RRKM Study of the Potential Energy Surface and Product Branching Ratios
- Author
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Gap-Sue Kim, Vadim V. Kislov, Alexander M. Mebel, and Ralf I. Kaiser
- Subjects
Reaction rate ,chemistry.chemical_compound ,Reaction rate constant ,Chemistry ,Ab initio quantum chemistry methods ,Computational chemistry ,Potential energy surface ,Tricarbon ,Ab initio ,Singlet state ,Physical and Theoretical Chemistry ,Cyclopropene - Abstract
Ab initio calculations of the potential energy surface for the C3(1Sigmag+)+C2H2(1Sigmag+) reaction have been performed at the RCCSD(T)/cc-pVQZ//B3LYP/6-311G(d,p) + ZPE[B3LYP/6-311G(d,p)] level with extrapolation to the complete basis set limit for key intermediates and products. These calculations have been followed by statistical calculations of reaction rate constants and product branching ratios. The results show the reaction to begin with the formation of the 3-(didehydrovinylidene)cyclopropene intermediate i1 or five-member ring isomer i7 with the entrance barriers of 7.6 and 13.8 kcal/mol, respectively. i1 rearranges to the other C5H2 isomers, including ethynylpropadienylidene i2, singlet pentadiynylidene i3, pentatetraenylidene i4, ethynylcyclopropenylidene i5, and four- and five-member ring structures i6, i7, and i8 by ring-closure and ring-opening processes and hydrogen migrations. i2, i3, and i4 lose a hydrogen atom to produce the most stable linear isomer of C5H with the overall reaction endothermicity of approximately 24 kcal/mol. H elimination from i5 leads to the formation of the cyclic C5H isomer, HC2C3, +H, 27 kcal/ mol above C3+C2H2. 1,1-H2 loss from i4 results in the linear pentacarbon C5+H2 products endothermic by 4 kcal/mol. The H elimination pathways occur without exit barriers, whereas the H2 loss from i4 proceeds via a tight transition state 26.4 kcal/mol above the reactants. The characteristic energy threshold for the reaction under single collision conditions is predicted be in the range of approximately 24 kcal/mol. Product branching ratios obtained by solving kinetic equations with individual rate constants calculated using RRKM and VTST theories for collision energies between 25 and 35 kcal/mol show that l-C5H+H are the dominant reaction products, whereas HC2C3+H and l-C5+H2 are minor products with branching ratios not exceeding 2.5% and 0.7%, respectively. The ethynylcyclopropenylidene isomer i5 is calculated to be the most stable C5H2 species, more favorable than triplet pentadiynylidene i3t by approximately 2 kcal/mol.
- Published
- 2007
21. Ab Initio/RRKM Study of Dissociation Mechanism of Benzene Trication
- Author
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T. S. Zyubin, S. H. Lin, Alexander M. Mebel, André D. Bandrauk, and Gap-Sue Kim
- Subjects
RRKM theory ,Chemistry ,Ab initio ,Coulomb explosion ,Kinetic energy ,Dissociation (chemistry) ,Computer Science Applications ,Reaction rate constant ,Computational Theory and Mathematics ,Fragmentation (mass spectrometry) ,Computational chemistry ,Physical chemistry ,Physical and Theoretical Chemistry ,Isomerization - Abstract
Density functional B3LYP /6-31 G (d,p) calculations have been performed in order to investigate isomerization and dissociation of [Formula: see text] in the ground electronic state, which are relevant to the Coulomb explosion mechanism of benzene. The results demonstrate that the benzene-like isomer of [Formula: see text], 1, can decompose through various pathways leading to distinct fragmentation products. The most kinetically favorable channel involves ring opening in 1 accompanied with 1,2-shifts of two hydrogen atoms followed by rotation around the middle C–C bond and dissociation to H 2 CCCH 2+ + H 2 CCCH + with exothermicity and the highest barrier of 100.2 and 38.4 kcal/mol, respectively. Several other product channels, including [Formula: see text], [Formula: see text], [Formula: see text], and [Formula: see text], share the same highest barrier for the initial ring opening step with the pathway producing H 2 CCCH 2+ + H 2 CCCH + but exhibit higher second highest barriers. Elimination of [Formula: see text] to form [Formula: see text] is 137.9 kcal/mol exothermic but the highest barrier on the pathway leading to these products is 53.0 kcal/mol. A simple proton elimination to produce [Formula: see text] is computed to be 82–84 kcal/mol exothermic and to depict a 64–65 kcal/mol barrier. RRKM calculations of rate constants for individual reaction steps assuming that the initial internal energy of 1 is 110 kcal/mol and solving kinetic master equations to obtain relative branching ratios show that H 2 CCCH 2+ + H 2 CCCH + are the dominant products (81.5%) followed by [Formula: see text] (13.2%) and the other minor products include [Formula: see text] (2.6%), [Formula: see text] (1.1%), [Formula: see text] (0.55%), [Formula: see text] (0.49%), [Formula: see text] (0.20%), and [Formula: see text] (0.14%). The fragments are expected to be produced with high translational energy due to high Coulomb repulsion energy barriers.
- Published
- 2003
22. Ab Initio/RRKM Study of the Potential Energy Surface of Triplet Ethylene and Product Branching Ratios of the C(3P) + CH4 Reaction
- Author
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Minh Tho Nguyen, Alexander M. Mebel, Gap Sue Kim, Sheng H. Lin, and Thanh Lam Nguyen
- Subjects
Reaction rate constant ,Computational chemistry ,Chemistry ,Elementary reaction ,Potential energy surface ,Ab initio ,Physical chemistry ,Quadratic configuration interaction ,Physical and Theoretical Chemistry ,Triplet state ,Isomerization ,Dissociation (chemistry) - Abstract
Calculations of the lowest triplet state potential energy surface for the C(3P) + CH4 reaction have been performed using the CCSD(T)/6-311+G(3df,2p)//QCISD/6-311G(d,p) method, and the microcanonical RRKM approach has been used to compute rate constants for individual reaction steps and product branching ratios. The results show that the reaction can occur by abstraction and insertion mechanisms. The abstraction pathway producing CH(2Π) + CH3(2A2‘ ‘) has a barrier of 26.9 kcal/mol relative to the reactants. The insertion leading to the HC−CH3(3A‘ ‘) intermediate via a 12.2 kcal/mol barrier followed by its isomerization to H2C−CH2(3A1) (through a 1,2 H shift) and/or by dissociation with an H-atom loss is found to be a more favorable mechanism. At a low excess internal energy originating from the collision energy (12.2 kcal/mol), the sole reaction products are C2H3 + H, where 90% of them are formed through the fragmentation of HC−CH3 and the rest (10%) are produced via the H2C−CH2 intermediate. At the higher...
- Published
- 2003
23. Ab initio study of excited electronic states and vibronic spectra of phenyl radical
- Author
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S. H. Lin, Alexander M. Mebel, and Gap-Sue Kim
- Subjects
Vibronic coupling ,Molecular geometry ,Absorption spectroscopy ,Ab initio quantum chemistry methods ,Chemistry ,Computational chemistry ,Molecular vibration ,Excited state ,Ab initio ,General Physics and Astronomy ,Vibronic spectroscopy ,Physical and Theoretical Chemistry ,Molecular physics - Abstract
Geometries, vibrational frequencies, excitation energies, and vibronic spectra of seven excited states of C6H5 have been studied by multireference ab initio calculations. For the 1 2 B 1 ,1 2 B 2 ,2 2 B 2 , and 2 2 B 1 states the most intense vibronic peaks are calculated at 17952, 37744, 43380, and 43251 cm −1 , respectively, and for 1 2 A 2 , 2 2 A 1 , and 3 2 A 1 upper estimates for adiabatic excitation energies are 22176, 30988, and 42543 cm −1 . We have assigned the 530–440 nm band in the absorption spectra to 1 2 B 1 with possible contribution from 1 2 A 2 , the 265–230 nm band to 1 2 B 2 and 3 2 A 1 , and intense peaks starting from ∼212 nm to 2 2 B 1 and 2 2 B 2 .
- Published
- 2002
24. Dissociation pathways of benzene trication
- Author
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André D. Bandrauk, Gap-Sue Kim, T. S. Zyubina, S. H. Lin, and Alexander M. Mebel
- Subjects
Reaction mechanism ,Coulomb explosion ,General Physics and Astronomy ,Photochemistry ,Medicinal chemistry ,Dissociation (chemistry) ,Dication ,chemistry.chemical_compound ,chemistry ,Ionization ,Cyclobutadiene ,Physical and Theoretical Chemistry ,Benzene ,Isomerization - Abstract
Density functional B3LYP calculations have been performed to investigate dissociation pathways of benzene trication in order to understand the mechanism of dissociative ionization of benzene after irradiation in intense laser fields. Numerous decomposition products can be formed: H 2 CCCH 2+ +C 3 H 3 + (with the activation barrier of 38.4 kcal/mol), cyclobutadiene dication C 4 H 4 2+ +C 2 H 2 + (53.0 kcal/mol), C 6 H 5 2+ +H + (64–65 kcal/mol), etc. The C 2 H 2 + detachment channels have the highest exothermicity (−131 to −138 kcal/mol), followed by C 3 H 3 + detachment (−125.7) and finally H + detachment (−83.7). The fragments are expected to be produced with high-translational energy due to high Coulomb repulsion energy barriers.
- Published
- 2002
25. A theoretical re-evaluation of the heat of formation of phenylcarbene
- Author
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Minh Tho Nguyen, Alexander M. Mebel, Thanh Lam Nguyen, and Gap-Sue Kim
- Subjects
Energy level splitting ,General Physics and Astronomy ,Standard enthalpy of formation ,Bond length ,chemistry.chemical_compound ,Molecular geometry ,chemistry ,Ab initio quantum chemistry methods ,Computational chemistry ,Physical chemistry ,Singlet state ,Physical and Theoretical Chemistry ,Methylene ,Carbene - Abstract
Singlet–triplet separation and heat of formation of phenylcarbene were calculated by using the B3LYP, RCCSD(T), G2M, G3, CASSCF, CASPT2 and MRCI methods. Our calculated values are 2.5±1 kcal/mol for the singlet–triplet splitting energy, 113.5±1 kcal/mol for the standard heat of formation (ΔH f 298 0 ) of singlet phenylcarbene, and 111.0±2 kcal/mol for the standard heat of formation of triplet phenylcarbene. While the singlet–triplet separation is in good agreement with previous theoretical and experimental data, the standard heat of formation of triplet phenylcarbene is about 7–8 kcal/mol higher than the experimental value (103.8±2.2 kcal/mol by Squires et al. [J. Chem. Soc., Perkin Trans. 2 (1999) 2249]).
- Published
- 2001
26. A theoretical study of the excited electronic states of the molecular ion BBr
- Author
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Gap-Sue Kim and David M. Hirst
- Subjects
Excited electronic state ,Chemistry ,Polyatomic ion ,Bound state ,Biophysics ,Atomic physics ,Physical and Theoretical Chemistry ,Spectroscopy ,Condensed Matter Physics ,Molecular Biology ,Dissociation (chemistry) ,Electronic states - Abstract
A comprehensive theoretical treatment is presented of the low-lying electronic states of the molecular ion BBr+ correlating with the two lowest dissociation asymptotes B+(1S) Br(2P) and B(2P)+Br+(3P). All-electron CASSCF+CI calculations have been made with averaged atomic natural orbital basis sets. Spectroscopic constants are calculated for the bound states but are in disagreement with an experimental analysis in the literature of a 2Πr → X 2Σ+ system. It is suggested that a re-examination of the spectroscopy of this species would be worthwhile.
- Published
- 1997
27. Ab initio potential-energy curves for excited electronic states of the molecular ion AsCl+
- Author
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David M. Hirst and Gap-Sue Kim
- Subjects
Excited electronic state ,Chemistry ,Polyatomic ion ,Bound state ,Ab initio ,General Physics and Astronomy ,Physical and Theoretical Chemistry ,Asymptote ,Atomic physics ,Potential energy ,Dissociation (chemistry) ,Electronic states - Abstract
This paper presents a comprehensive theoretical treatment of the low-lying electronic states of the molecular ion AsCl+ correlating with the lowest dissociation asymptote As+ (3P) + Cl (2P). All-electron CASSCF + CI calculations have been made with averaged atomic natural orbital basis sets. There are four bound states, namely X2Π, A2Π, 1 4 Σ − and 1 4 Π . Spectroscopic constants are calculated for the bound states and are in good agreement with experimental data for the doublet states.
- Published
- 1997
28. Solvent migration from the C- to the N-terminus of amino acid in photoionization of phenylglycine-water complex.
- Author
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Hyung Min Kim, Kyu Young Han, Juyeon Park, Gap-Sue Kim, and Seong Keun Kim
- Subjects
AMINO acid sequence ,PHOTOIONIZATION ,PERTURBATION theory ,CARBOXYLIC acids ,DECARBOXYLATION ,PHOTOCHEMISTRY - Abstract
Photo-oxidation of amino acids is known to generate reactive protein radicals that lead to lethal disorders. We investigated photoionization of hydrated phenylglycine complexes in the gas phase and found that the excess internal energy from photoionization drives decarboxylation in competition with dehydration. We also found that, in decarboxylation, the solvent migrates a large distance from the C terminus of the neutral amino acid to the N terminus of the newly formed radical cation upon ionization, prior to the departure of the carboxyl group. It is noted that a solvent does not just act as a passive medium bound to the solute molecule but actively pursues its own course of action upon external perturbation that changes its chemical environment. [ABSTRACT FROM AUTHOR]
- Published
- 2008
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29. Anab initostudy of the excited states of the molecular ions NF+and PCl+
- Author
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David M. Hirst and Gap-Sue Kim
- Subjects
Valence (chemistry) ,Chemistry ,Biophysics ,Condensed Matter Physics ,Dissociation (chemistry) ,Ion ,Electronic states ,Computational chemistry ,Excited state ,Bound state ,Physical chemistry ,Physical and Theoretical Chemistry ,Ab inito ,Molecular Biology - Abstract
This paper presents a comprehensive theoretical treatment of the low-lying electronic states of the molecular ions NF+ and PCl+ correlating with the lowest dissociation asymptote N+, P+ (3P) + F, Cl(2P). CASSCF + CI calculations have been made with the correlation-consistent valence quadruple-zeta basis sets. Relatively few states (X2Π, A2Π, 14Σ-, 14Π) are bound. Spectroscopic constants are calculated for the bound states, and it is suggested that the A2Π → X2Π system should be observable for NF+.
- Published
- 1995
30. Excited states of the PF+and NCl+ions: a theoretical treatment
- Author
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David M. Hirst and Gap-Sue Kim
- Subjects
Valence (chemistry) ,Chemistry ,Excited state ,Bound state ,Biophysics ,Physical and Theoretical Chemistry ,Atomic physics ,Condensed Matter Physics ,Molecular Biology ,Potential energy ,Electronic states ,Ion - Abstract
This paper presents a comprehensive theoretical treatment of the low-lying electronic states of the molecular ions PF+ and NCl+. CASSCF + CI calculations have been made with the correlation-consistent valence triple-zeta basis sets. For PF+ only four states (X 2Π, A 2Σ+, 1 4Π, 1 4Σ-) states have bound potential energy curves. In the case of NCl+ there are many more bound states, namely X 2Π, 2 2Π, 3 2Π, 2 2Σ+, 2 2Σ-, 2Δ, 1 4Π, 1 4Σ-. Spectroscopic constants have been calculated for these states and should be reasonable predictions for the experimental values.
- Published
- 1995
31. The reaction of phenyl radical with molecular oxygen: a G2M study of the potential energy surface
- Author
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Vadim V. Kislov, Alexander M. Mebel, I. V. Tokmakov, Gap Sue Kim, and Ming-Chang Lin
- Subjects
Exothermic reaction ,Molecular Structure ,Chemistry ,Radical ,Thermal decomposition ,Ab initio ,Benzene ,Photochemistry ,Reaction rate ,Oxygen ,Cyclopentadienyl complex ,Models, Chemical ,Phenols ,Potential energy surface ,Benzoquinones ,Molecule ,Physical and Theoretical Chemistry ,Furans ,Reactive Oxygen Species ,Pyrans ,Signal Transduction - Abstract
Ab initio G2M calculations have been performed to investigate the potential energy surface for the reaction of C6H5 with O2. The reaction is shown to start with an exothermic barrierless addition of O2 to the radical site of C6H5 to produce phenylperoxy (1) and, possibly, 1,2-dioxaspiro[2.5]octadienyl (dioxiranyl, 8) radicals. Next, 1 loses the terminal oxygen atom to yield the phenoxy + O products (3) or rearranges to 8. The dioxiranyl can further isomerize to a seven-member ring 2-oxepinyloxy radical (10), which can give rise to various products including C5H5 + CO2, pyranyl + CO, o-benzoquinone + H, and 2-oxo-2,3-dihydrofuran-4-yl + C2H2. Once 10 is produced, it is unlikely to go back to 8 and 1, because the barriers separating 10 from the products are much lower than the reverse barrier from 10 to 8. Thus, the branching ratio of C6H5O + O against the other products is mostly controlled by the critical transition states between 1 and 3, 1 and 8, and 8 and 10. According to the calculated barriers, the most favorable product channel for the decomposition of 10 is C5H5 + CO2, followed by pyranyl + CO and o-benzoquinone + H. Since C6H5O + O and C5H5 + CO2 are expected to be the major primary products of the C6H5 + O2 reaction and thermal decomposition of C6H5O leads to C5H5 + CO, cyclopentadienyl radicals are likely to be the major product of phenyl radical oxidation, and so it results in degradation of the six-member aromatic ring to the five-member cyclopentadienyl ring. Future multichannel RRKM calculations of reaction rate constants are required to support these conclusions and to quantify the product branching ratios at various combustion conditions.
- Published
- 2006
32. The Reaction of Tricarbon with Acetylene: An Ab Initio/RRKM Study of the Potential Energy Surface and Product Branching Ratios.
- Author
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Alexander M. Mebel, Gap-Sue Kim, Vadim V. Kislov, and Ralf I. Kaiser
- Subjects
- *
PHYSICAL & theoretical chemistry , *SCIENCE , *CHEMISTRY , *PHYSICAL sciences - Abstract
Ab initio calculations of the potential energy surface for the C3(1g) C2H2(1g) reaction have been performed at the RCCSD(T)/cc-pVQZ//B3LYP/6-311G(d,p) ZPEB3LYP/6-311G(d,p) level with extrapolation to the complete basis set limit for key intermediates and products. These calculations have been followed by statistical calculations of reaction rate constants and product branching ratios. The results show the reaction to begin with the formation of the 3-(didehydrovinylidene)cyclopropene intermediate i1or five-member ring isomer i7with the entrance barriers of 7.6 and 13.8 kcal/mol, respectively. i1rearranges to the other C5H2isomers, including ethynylpropadienylidene i2, singlet pentadiynylidene i3, pentatetraenylidene i4, ethynylcyclopropenylidene i5, and four- and five-member ring structures i6, i7, and i8by ring-closure and ring-opening processes and hydrogen migrations. i2, i3, and i4lose a hydrogen atom to produce the most stable linear isomer of C5H with the overall reaction endothermicity of ∼24 kcal/mol. H elimination from i5leads to the formation of the cyclic C5H isomer, HC2C3, H, 27 kcal/ mol above C3C2H2. 1,1-H2loss from i4results in the linear pentacarbon C5H2products endothermic by 4 kcal/mol. The H elimination pathways occur without exit barriers, whereas the H2loss from i4proceeds via a tight transition state 26.4 kcal/mol above the reactants. The characteristic energy threshold for the reaction under single collision conditions is predicted be in the range of ∼24 kcal/mol. Product branching ratios obtained by solving kinetic equations with individual rate constants calculated using RRKM and VTST theories for collision energies between 25 and 35 kcal/mol show that l-C5H H are the dominant reaction products, whereas HC2C3H and l-C5H2are minor products with branching ratios not exceeding 2.5% and 0.7%, respectively. The ethynylcyclopropenylidene isomer i5is calculated to be the most stable C5H2species, more favorable than triplet pentadiynylidene i3tby ∼2 kcal/mol. [ABSTRACT FROM AUTHOR]
- Published
- 2007
- Full Text
- View/download PDF
33. Ab initio investigations on the HOSO[sub 2]+O[sub 2]→SO[sub 3]+HO[sub 2] reaction.
- Author
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Majumdar, D., Kim, Gap-Sue, Gap-Sue Kim, Kim, Jongseob, Jongseob Kim, Oh, Kyung Seok, Kyung Seok Oh, Lee, Jin Yong, Jin Yong Lee, Kim, Kwang S., Choi, Won Yong, Won Yong Choi, Lee, Sung-Hoon, Sung-Hoon Lee, Kang, Myung-Ho, Myung-Ho Kang, Mhin, Byung Jin, and Byung Jin Mhin
- Subjects
CHEMICAL reactions ,RADICALS (Chemistry) ,HYDROGEN ,SULFUR compounds - Abstract
HOSO[sub 2] radical is the key intermediate for the oxidation SO[sub 2] to SO[sub 3] by OH radical in the atmosphere. The structural aspects and the energetics of the reaction HOSO[sub 2]+O[sub 2]→SO[sub 3]+HO[sub 2] have been studied using Mo\ller-Plesset (MP2) and density functional (DFT) techniques with 6-31G[sup **] and triple-ζ, quadruple-ζ, and quintuple-ζ quality basis sets including diffuse basis functions. The detailed theoretical analyses have further revealed that this reaction could proceed through the formation of intermediate complexes and an intramolecular proton transfer like transition state. The energetics of these intermediate reactions has been studied in detail. The use of MP2 methods to study such radical mechanisms had some characteristic symmetry-breaking problem with larger basis sets. This unphysical situation with larger basis set MP2 calculations in this hypervalent system has been explained through the interpretation of the relevant energy surface. © 2000 American Institute of Physics. [ABSTRACT FROM AUTHOR]
- Published
- 2000
- Full Text
- View/download PDF
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