title: A ground state morphed intermolecular potential for the hydrogen bonded and van der Waals isomers in OC:HI and a prediction of an anomalous deuterium isotope effect.
abstract: An extended analysis of the noncovalent interaction OC:HI is reported using microwave and infrared supersonic jet spectroscopic techniques. All available spectroscopic data then provide the basis for generating an accurately determined vibrationally complete semiempirical intermolecular potential function using a four-dimensional potential coordinate morphing methodology. These results are consistent with the existence of four bound isomers: OC-HI, OC-IH, CO-HI, and CO-IH. Analysis also leads to unequivocal characterization of the common isotopic ground state as having the OC-HI structure and with the first excited state having the OC-IH structure with an energy of 3.4683(80) cm(-1) above the ground state. The potential is consistent with the following barriers between the pairs of isomers: 382(4) cm(-1) (OC-IH/OC-HI), 294(5) cm(-1) (CO-IH/CO-HI), 324(3) cm(-1) (OC-IH/CO-IH), and 301(2) cm(-1) (OC-HI/CO-HI) defined with respect to each lower minimum. The potential is also determined to have a linear OC-IH van der Waals global equilibrium minimum structure having R(e)=4.180(11) Å, θ(1)=0.00(1)°, and θ(2)=0.00(1)°. This is differentiated from its OC-HI ground state hydrogen bound structure having R(0)=4.895(1) Å, θ(1)=20.48(1)°, and θ(2)=155.213(1)° where the distances are defined between the centers of mass of the monomers and θ(1) and θ(2) as cos(-1)[<cos(2) θ(i)>(1/2)] for i=1 and 2. A fundamentally new molecular phenomenon - ground state isotopic isomerization is proposed based on the generated semiempirical potential. The protonated ground state hydrogen-bonded OC-HI structure is predicted to be converted on deuteration to the corresponding ground state van der Waals OC-ID isomeric structure. This results in a large anomalous isotope effect in which the R(0) center of mass distance between monomeric components changes from 4.895(1) to 4.286(1) Å. Such a proposed isotopic effect is demonstrated to be a consequence of differential zero point energy factors resulting from the shallower nature of hydrogen bonding at a local potential minimum (greater quartic character of the potential) relative to the corresponding van der Waals global minimum. Further consequences of this anomalous deuterium isotope effect are also discussed.
authors.affiliation: Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, USA.
authors.forename: Luis A
authors.initials: LA
authors.lastname: Rivera-Rivera
authors.forename: Zhongcheng
authors.initials: Z
authors.lastname: Wang
authors.forename: Blake A
authors.initials: BA
authors.lastname: McElmurry
authors.forename: Fabrice F
authors.initials: FF
authors.lastname: Willaert
authors.forename: Robert R
authors.initials: RR
authors.lastname: Lucchese
authors.forename: John W
authors.initials: JW
authors.lastname: Bevan
authors.forename: Richard D
authors.initials: RD
authors.lastname: Suenram
authors.forename: Frank J
authors.initials: FJ
authors.lastname: Lovas