Theory for Vibrationally Resolved Two-Photon Circular Dichroism Spectra. Application to (R)-(+)-3-Methylcyclopentanone

被引：47

作者：

Lin, Na ^{[2
,3
]}

Santoro, Fabrizio ^{[1
]}

Rizzo, Antonio ^{[1
]}

Luo, Yi ^{[2
]}

Zhao, Xian ^{[3
]}

Barone, Vincenzo ^{[1
]}

机构：

[1] IPCF CNR, Area Ric, I-56124 Pisa, Italy

[2] Royal Inst Technol, Dept Theoret Chem, Sch Biotechnol, SE-10691 Stockholm, Sweden

[3] Shandong Univ, Inst Crystal Mat, Jinan 250100, Peoples R China

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2009年 / 113卷 / 16期

基金：

中国国家自然科学基金;

关键词：

CHIRAL MOLECULES; FRANCK-CONDON; MULTIPHOTON ABSORPTION; EXCHANGE; DENSITY; LIQUID; SPECTROSCOPY; SIMULATIONS; PERMANENT; ETHYLENE;

D O I：

10.1021/jp8105925

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

A harmonic adiabatic approach in combination with density functional response theory for computing two-photon vibronically resolved circular dichroism spectra of chiral molecules is presented. It includes both Franck-Condon and Herzberg-Teller contributions and it takes fully into account frequency changes and Duschinsky effects. Model calculations have been performed for two dominant conformers of (R)-(+)-3-methylcyclopentanone in the gas phase. It is found that the Herzberg-Teller contribution can introduce a sign change in two-photon circular dichroism of a single excited electronic state of a conformer. The change survives after Boltzmann averaging, and it might be amenable to experimental verification. Interesting interference effects between Franck-Condon and Herzberg-Teller contributions are revealed and analyzed in detail. Results obtained within the more approximate and less computationally intensive linear coupling vibronic model are also given for comparison.

引用

页码：4198 / 4207

页数：10

共 22 条

[21] Determination of absolute configurations of N-Formyl-3,3',4,4'-tetrahydrospiro[naphthalene-1(2H),2'(1'H)-pyridine] (2) and N-Formyl-3',4'-dihydrospiro[indan-1,2'(1'H)-pyridine] (3) by analysis of circular dichroism spectra. A case of two compounds with similar configuration but nearly mirror image CD spectra
Ripa, L
Hallberg, A
Sandstrom, J
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (24) : 5701 - 5705
[22] Semiclassical theory of two-photon polarization-dependent fractional optical collisions:: Application to the Mg-He(3s2 1S0→3p 1P1→5s 1S0, 4d 1D2) optical collision
Kupriyanov, DV
Sokolov, IM
Slavgorodskii, AV
Trubilko, AI
PHYSICAL REVIEW A, 1999, 60 (03): : 2230 - 2254

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