VIBRATIONAL-ENERGY DYNAMICS OF HYDROGEN-BONDED PYRROLE COMPLEXES

被引：37

作者：

GRUBBS, WT ^{[1
]}

DOUGHERTY, TP ^{[1
]}

HEILWEIL, EJ ^{[1
]}

机构：

[1] NIST,DIV MOLEC PHYS,GAITHERSBURG,MD 20899

来源：

JOURNAL OF PHYSICAL CHEMISTRY | 1995年 / 99卷 / 27期

关键词：

D O I：

10.1021/j100027a007

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：

Picosecond IR transient bleaching and double-resonance absorption experiments were performed on the pyrrole (C4H5N) NH stretching vibration of solution phase hydrogen-bonded pyrrole:base complexes in room temperature CCl4. Population lifetime (T-1) measurements show that hydrogen-bonding interactions enhance the vibrational energy relaxation rate of the NH functional group significantly, and the magnitude of this enhancement increases monotonically with proton-accepting strength of the base suggesting it is independent of base vibrational structure. Values for the NH stretch (v = 1) T lifetime include 49 +/- 3 ps (1 sigma) for ''free'' pyrrole, 13 +/- 2 ps for pyrrole:acetonitrile, and 4.5 +/- 0.4 ps for pyrrole:tetrahydrofuran complexes. Intramolecular vibrational energy transfer is the dominant relaxation pathway, but the results suggest a weak pump-induced dissociation channel. Extracted T-1 lifetimes differ markedly from earlier values obtained by transient anti-Stokes Raman methods.

引用

页码：10716 / 10722

页数：7

共 28 条

[1] PATHWAYS OF RELAXATION OF THE N-H STRETCHING VIBRATION OF PYRROLE IN LIQUIDS [J].