What factors determine whether a proton-bound homodimer has a symmetric or an asymmetric hydrogen bond?

被引:23
作者
Chan, Bun [1 ,2 ]
Del Bene, Janet E. [3 ]
Radom, Leo [1 ,2 ]
机构
[1] Univ Sydney, Sch Chem, Sydney, NSW 2006, Australia
[2] Univ Sydney, Ctr Excellence Free Radical Chem & Biotechnol, Sydney, NSW 2006, Australia
[3] Youngstown State Univ, Dept Chem, Youngstown, OH 44555 USA
基金
美国国家科学基金会;
关键词
hydrogen bonding; quantum chemical calculations; homodimers; ab initio; BINDING-ENERGIES; GAUSSIAN-3; G3; MOLECULES; ACCEPTOR; DONOR;
D O I
10.1080/00268970902740571
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
What factors determine whether a proton-bound homodimer with a central [X center dot center dot center dot H center dot center dot center dot X](1) moiety has a symmetric or an asymmetric hydrogen bond? Although hydrogen bonding may be considered the incipient step of protonation, quantum chemical computations indicate that the proton affinity of the base is not the governing influence as to whether the hydrogen bond is symmetric or asymmetric. Instead, the primary factor appears to be the electronegativity of the hydrogen-bonded heavy atom X, with a more electronegative X usually facilitating the formation of a symmetric hydrogen bond. Additional influences arise from the increased weakening of the X-H bond in the protonated monomer upon dimer formation for less electronegative X, as well as from stabilizing or destabilizing interactions involving more distant atoms that do not directly participate in the [X center dot center dot center dot H center dot center dot center dot X](+) hydrogen bond.
引用
收藏
页码:1095 / 1105
页数:11
相关论文
共 41 条
[1]  
[Anonymous], 2016, GAUSSIAN 16 REV B01
[2]  
[Anonymous], 1960, The Nature of the Chemical Bond, 3rd ed
[3]  
[Anonymous], 1997, HYDROGEN BONDING THE
[4]   Proton donor is more important than proton acceptor in hydrogen bond formation: A universal equation for calculation of hydrogen bond strength [J].
Bian, L .
JOURNAL OF PHYSICAL CHEMISTRY A, 2003, 107 (51) :11517-11524
[5]   The hydrogen bond [J].
Buckingham, A. D. ;
Del Bene, J. E. ;
McDowell, S. A. C. .
CHEMICAL PHYSICS LETTERS, 2008, 463 (1-3) :1-10
[6]   FROM CRYSTAL STATICS TO CHEMICAL-DYNAMICS [J].
BURGI, HB ;
DUNITZ, JD .
ACCOUNTS OF CHEMICAL RESEARCH, 1983, 16 (05) :153-161
[7]  
BURGI HB, 1994, STRUCTURE CORRELATIO, V1, P197
[8]   Proton-bound homodimers: How are the binding energies related to proton affinities? [J].
Chan, Bun ;
Del Bene, Janet E. ;
Radom, Leo .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (40) :12197-12199
[9]   Gaussian-3 (G3) theory for molecules containing first and second-row atoms [J].
Curtiss, LA ;
Raghavachari, K ;
Redfern, PC ;
Rassolov, V ;
Pople, JA .
JOURNAL OF CHEMICAL PHYSICS, 1998, 109 (18) :7764-7776
[10]   Gaussian-3 theory using reduced Moller-Plesset order [J].
Curtiss, LA ;
Redfern, PC ;
Raghavachari, K ;
Rassolov, V ;
Pople, JA .
JOURNAL OF CHEMICAL PHYSICS, 1999, 110 (10) :4703-4709