title: Quantification of hyperconjugative effect on the proton donor X-H bond length changes in the red- and blueshifted hydrogen-bonded complexes.
abstract: A whole dataset containing 55 hydrogen bonds were studied at the MP2/aug-cc-pVTZ level of theory. The changes of geometries and stretching vibrational frequencies show that there are 31 redshifted and 24 blueshifted hydrogen-bonded complexes. Natural bond orbital analysis was carried out at the B3LYP/aug-cc-pVTZ level of theory to obtain the electron densities in the bonding and antibonding orbitals of the proton donor X-H bond, which are closely associated with its bond length. Based on their relationship, a generally applicable method considering both the electron densities in the bonding and antibonding orbitals of the proton donor X-H bond has been developed to quantitatively describe the hyperconjugative effect on the X-H bond length changes in these hydrogen-bonded complexes.
authors.affiliation: Department of Chemistry, State Key Laboratory of Applied Organic Chemistry, Lanzhou University, 222 South Tianshui Road, 730000, Lanzhou, People's Republic of China. zhoupp07@lzu.edu.cn
authors.forename: Pan-Pan
authors.initials: PP
authors.lastname: Zhou
authors.forename: Wen-Yuan
authors.initials: WY
authors.lastname: Qiu
authors.forename: Neng-Zhi
authors.initials: NZ
authors.lastname: Jin
mesh_terms: D006860:Hydrogen Bonding; D011522:Protons; D011789:Quantum Theory; D014732:Vibration
chemical_list: D011522:Protons