| Item type |
デフォルトアイテムタイプ_（フル）(1) |
| 公開日 |
2023-03-18 |
| タイトル |
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|
タイトル |
Franck-Condon factors based on anharmonic vibrational wave functions of polyatomic molecules |
|
言語 |
en |
| 作成者 |
Rodriguez-Garcia, Valerie
Yagi, Kiyoshi
Hirao, Kimihiko
Iwata, Suehiro
Hirata, So
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| アクセス権 |
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アクセス権 |
open access |
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アクセス権URI |
http://purl.org/coar/access_right/c_abf2 |
| 権利情報 |
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権利情報 |
Copyright (c) 2006 American Institute of Physics. |
| 主題 |
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主題Scheme |
Other |
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主題 |
Franck-Condon factors |
| 主題 |
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主題Scheme |
Other |
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主題 |
vibrational states |
| 主題 |
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主題Scheme |
Other |
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主題 |
wave functions |
| 主題 |
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主題Scheme |
Other |
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主題 |
SCF calculations |
| 主題 |
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主題Scheme |
Other |
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主題 |
configuration interactions |
| 主題 |
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主題Scheme |
Other |
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主題 |
harmonic oscillators |
| 主題 |
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主題Scheme |
Other |
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主題 |
molecular electronic states |
| 主題 |
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主題Scheme |
Other |
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主題 |
coupled cluster calculations |
| 主題 |
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主題Scheme |
Other |
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主題 |
perturbation theory |
| 主題 |
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主題Scheme |
Other |
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主題 |
photoelectron spectra |
| 主題 |
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主題Scheme |
Other |
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主題 |
water |
| 主題 |
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主題Scheme |
Other |
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主題 |
positive ions |
| 主題 |
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主題Scheme |
Other |
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主題 |
organic compounds |
| 主題 |
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主題Scheme |
Other |
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主題 |
spectral line intensity |
| 主題 |
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主題Scheme |
Other |
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主題 |
potential energy surfaces |
| 内容記述 |
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内容記述 |
Franck-Condon (FC) integrals of polyatomic molecules are computed on the basis of vibrational self-consistent-field (VSCF) or configuration-interaction (VCI) calculations capable of including vibrational anharmonicity to any desired extent (within certain molecular size limits). The anharmonic vibrational wave functions of the initial and final states are expanded unambiguously by harmonic oscillator basis functions of normal coordinates of the respective electronic states. The anharmonic FC integrals are then obtained as linear combinations of harmonic counterparts, which can, in turn, be evaluated by established techniques taking account of the Duschinsky rotations, geometry displacements, and frequency changes. Alternatively, anharmonic wave functions of both states are expanded by basis functions of just one electronic state, permitting the FC integral to be evaluated directly by the Gauss-Hermite quadrature used in the VSCF and VCI steps [Bowman et al., Mol. Phys. 104, 33 (2006)]. These methods in conjunction with the VCI and coupled-cluster with singles, doubles, and perturbative triples [CCSD(T)] method have predicted the peak positions and intensities of the vibrational manifold in the X̃ 2B1 photoelectron band of H2O with quantitative accuracy. It has revealed that two weakly visible peaks are the result of intensity borrowing from nearby states through anharmonic couplings, an effect explained qualitatively by VSCF and quantitatively by VCI, but not by the harmonic approximation. The X̃ 2B2 photoelectron band of H2CO is less accurately reproduced by this method, likely because of the inability of CCSD(T)/ cc-pVTZ to describe the potential energy surface of open-shell H2CO+ with the same high accuracy as in H2O+. |
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言語 |
en |
| 出版者 |
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出版者 |
American Institute of Physics |
| 言語 |
|
|
言語 |
eng |
| 資源タイプ |
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資源タイプ識別子 |
http://purl.org/coar/resource_type/c_6501 |
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資源タイプ |
journal article |
| 出版タイプ |
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|
出版タイプ |
VoR |
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出版タイプResource |
http://purl.org/coar/version/c_970fb48d4fbd8a85 |
| 関連情報 |
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識別子タイプ |
DOI |
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関連識別子 |
10.1063/1.2209676 |
| 関連情報 |
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|
識別子タイプ |
DOI |
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|
関連識別子 |
http://dx.doi.org/10.1063/1.2209676 |
| 収録物識別子 |
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収録物識別子タイプ |
ISSN |
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収録物識別子 |
0021-9606 |
| 収録物識別子 |
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収録物識別子タイプ |
NCID |
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収録物識別子 |
AA00694991 |
| 開始ページ |
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開始ページ |
014109-1 |
| 書誌情報 |
Journal of Chemical Physics
Journal of Chemical Physics
巻 125,
号 1,
p. 014109-1-014109-9,
発行日 2006-07-07
|
| 旧ID |
19504 |
JChemPhys_125_014109.pdf (161.9 KB)
