title: The interplay of hydrogen bonding and dispersion in phenol dimer and trimer: structures from broadband rotational spectroscopy.
abstract: The structures of the phenol dimer and phenol trimer complexes in the gas phase have been determined using chirped-pulse Fourier transform microwave spectroscopy in the 2-8 GHz band. All fourteen (13)C and (18)O phenol dimer isotopologues were assigned in natural abundance. A full heavy atom experimental substitution structure was determined, and a least-squares fit ground state r0 structure was determined by proper constraint of the M06-2X/6-311++g(d,p) ab initio structure. The structure of phenol dimer features a water dimer-like hydrogen bond, as well as a cooperative contribution from inter-ring dispersion. Comparisons between the experimental structure and previously determined experimental structures, as well as ab initio structures from various levels of theory, are discussed. For phenol trimer, a C3 symmetric barrel-like structure is found, and an experimental substitution structure was determined via measurement of the six unique (13)C isotopologues. The least-squares fit rm((1)) structure reveals a similar interplay between hydrogen bonding and dispersion in the trimer, with water trimer-like hydrogen bonding and C-H···π interactions.
authors.affiliation: Department of Chemistry, University of Virginia, McCormick Road, Charlottesville, Virginia 22904, USA.
authors.forename: Nathan A
authors.initials: NA
authors.lastname: Seifert
authors.forename: Amanda L
authors.initials: AL
authors.lastname: Steber
authors.forename: Justin L
authors.initials: JL
authors.lastname: Neill
authors.forename: Cristóbal
authors.initials: C
authors.lastname: Pérez
authors.forename: Daniel P
authors.initials: DP
authors.lastname: Zaleski
authors.forename: Brooks H
authors.initials: BH
authors.lastname: Pate
authors.forename: Alberto
authors.initials: A
authors.lastname: Lesarri
mesh_terms: D019281:Dimerization; D005583:Fourier Analysis; D006860:Hydrogen Bonding; D008872:Microwaves; D015394:Molecular Structure; D019800:Phenol / Q000737:chemistry*; D011789:Quantum Theory; D012399:Rotation; D013057:Spectrum Analysis
chemical_list: D019800:Phenol