Crossover from hydrogen to chemical bonding

被引：218

作者：

Dereka, Bogdan ^{[1
,2
]}

Yu, Qi ^{[3
,4
,5
]}

Lewis, Nicholas H. C. ^{[1
,2
]}

Carpenter, William B. ^{[1
,2
]}

Bowman, Joel M. ^{[3
,4
]}

Tokmakoff, Andrei ^{[1
,2
]}

机构：

[1] Univ Chicago, Dept Chem, Inst Biophys Dynam, Chicago, IL 60637 USA

[2] Univ Chicago, James Franck Inst, Chicago, IL 60637 USA

[3] Emory Univ, Dept Chem, Atlanta, GA 30322 USA

[4] Emory Univ, Cherry L Emerson Ctr Sci Computat, Atlanta, GA 30322 USA

[5] Yale Univ, Dept Chem, New Haven, CT 06520 USA

来源：

SCIENCE | 2021年 / 371卷 / 6525期

基金：

美国国家科学基金会; 瑞士国家科学基金会;

关键词：

SPECTROSCOPY; ENERGIES; SPECTRUM;

D O I：

10.1126/science.abe1951

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

Hydrogen bonds (H-bonds) can be interpreted as a classical electrostatic interaction or as a covalent chemical bond if the interaction is strong enough. As a result, short strong H-bonds exist at an intersection between qualitatively different bonding descriptions, with few experimental methods to understand this dichotomy. The [F-H-F](-) ion represents a bare short H-bond, whose distinctive vibrational potential in water is revealed with femtosecond two-dimensional infrared spectroscopy. It shows the superharmonic behavior of the proton motion, which is strongly coupled to the donor-acceptor stretching and disappears on H-bond bending. In combination with high-level quantum-chemical calculations, we demonstrate a distinct crossover in spectroscopic properties from conventional to short strong H-bonds, which identify where hydrogen bonding ends and chemical bonding begins.

引用

页码：160 / +

页数：5

共 34 条

[1] Direct evidence of a low barrier hydrogen bond in the catalytic triad of a Serine protease [J].