Correlation effects in the two-dimensional vibrational spectroscopy of coupled vibrations

被引：66

作者：

Demirdöven, N ^{[1
]}

Khalil, M ^{[1
]}

Golonzka, O ^{[1
]}

Tokmakoff, A ^{[1
]}

机构：

[1] MIT, Dept Chem, Cambridge, MA 02139 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2001年 / 105卷 / 34期

关键词：

D O I：

10.1021/jp011215d

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：

Correlated energy shifts in the spectral broadening of coupled vibrational transitions are shown to have clear signatures in infrared two-dimensional dispersed vibrational echo (DVE) spectroscopy. A model that includes correlation effects through a correlation coefficient (rho) for a bivariate distribution is used to describe two-dimensional experiments on the coupled carbonyl stretches of Rh(CO)(2)(C5H7O2) (or RDC) in chloroform. Signatures of correlated (0 < rho < +1) and anticorrelated (-1 < rho < 0) broadening in DVE experiments manifest themselves in the depth of modulation of the signal and the magnitude of the echo peak shift. For the case of RDC, the broadening is highly correlated (rho = 0.9) and can be explained in terms of the solvent-induced modulation of the Rh electron density.

引用

页码：8025 / 8030

页数：6

共 47 条

[1] Three pulse photon echo peak shift study of the B800 band of the LH2 complex of Rps. acidophila at room temperature:: A coupled master equation and nonlinear optical response function approach [J].