VIBRATIONAL AND ROTATIONAL RELAXATION-TIMES OF SOLVATED MOLECULAR-IONS

被引:155
作者
LI, M
OWRUTSKY, J
SARISKY, M
CULVER, JP
YODH, A
HOCHSTRASSER, RM
机构
[1] Department of Chemistry, University of Pennsylvania, Philadelphia
[2] Naval Research Laboratory, Washington
[3] Physics Department, University of Pennsylvania, Philadelphia
关键词
D O I
10.1063/1.464899
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
Infrared pump-probe and infrared polarization spectroscopy have been used to measure the vibrational relaxation times (T1) of the antisymmetric stretching mode and the reorientation times (T(R)) for N3-, NCS-, and NCO in D2O and/or methanol. For N3-, experiments were also conducted in H2O and hexamethyl-phosphamide (HPMA) solutions. The rapid vibrational relaxation and slow reorientation observed demonstrate strong coupling between the ions and the solvents. Longer vibrational relaxation and shorter reorientation times measured for NCS- reveal weaker solvent interactions that may be due to the importance of the charge distribution and the form of the normal coordinate. A comparison of the T1 and T(R) times in different solvents permits a determination of the relative interaction strengths for the solvents investigated. The relatively weaker coupling of N3- in the aprotic solvent HMPA demonstrates the importance of hydrogen bonding in strong solvent interactions in ionic solutions. The experimental results are compared with recent molecular dynamics simulations of ionic solutions.
引用
收藏
页码:5499 / 5507
页数:9
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