Effect of vibrational coherence on rotational dynamics in solution

✍ Scribed by S. Gnanakaran; R. M. Hochstrasser

• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 328 KB
• Volume: 72
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/(sici)1097-461x(1999)72:4<451::aid-qua28>3.0.co;2-p

✦ Synopsis

Nonequilibrium molecular dynamics simulations were used to investigate solvent effects on wavepacket motion and vibration᎐rotation coupling, using Ž . mercury iodide HgI , as an example. This work is inspired by the experimental study on the photolysis of HgI in ethanol where the vibrational wavepacket motion was observed 2 on the rotational dynamics of the HgI photoproduct. The wavepacket dynamics is Ž . evaluated from classical molecular dynamics MD simulations. The time evolution of the HgI internuclear distance distribution was used to examine the effect of anharmonicity and internuclear distance dependent charges on the wavepacket motion and its influence on the rotational dynamics. A key result of the present work is the discovery that the nonadiabatic solvation, which arises from the dynamics of the variations in partial charges of HgI with internuclear distance, is an important factor in accounting for the known behavior of coherently generated HgI.