Origin invariant approaches to the calculation of two-photon circular dichroism.
The origin dependence of the expression of two-photon circular dichroism in the length formulation employed by the authors in a recent computational study [B. Jansik et al., Chem. Phys. Lett. 414, 461 (2005)] is discussed in detail, and some inherently origin invariant alternative formulations are introduced. Extensive computational tests on a small reference chiral system, namely, a chiral form of H(2)O(2), are performed at the density functional theory (DFT)/B3LYP level of theory with large diffuse correlation consistent basis sets. The results indicate that the velocity formulation originally proposed by Tinoco, Jr. [J. Chem. Phys. 62, 1006 (1975)] provides the most convenient approach for an origin invariant calculation of two-photon circular dichroism.
Rizzo
Antonio
A
Istituto per i Processi Chimico-Fisici del Consiglio Nazionale delle Ricerche (IPCF-CNR), Area della Ricerca, via G. Moruzzi 1, I-56124 Pisa, Italy. rizzo@ipcf.cnr.it
Jansík
Branislav
B
Pedersen
Thomas Bondo
TB
Agren
Hans
H