Abstract:The linear and quadratic rotational Zeeman effect in HOF has been observed with a high magnetic field. The magnetic susceptibility anisotropies are 2χaa −χbb −χcc = (−19.6±0.6) × 10−6 erg/G2·mole and 2χbb −χaa −χcc = 12.8±1.2 (the a axis is nearly along the OF bond and the c axis is perpendicular to the molecular plane); the molecular g values are gaa = 0.642±0.001, gbb = −0.119±0.001, and gcc = −0.061±0.001 and the molecular quadrupole moments are Qaa = (0.2±0.4)×10−26 esu · cm2, Qbb = 1.9±0.8, and Qcc = −2.1… Show more
“… 1 Optimized structures of (a) FOH ( C s ), (b) the (FOH) 2 minimum energy complex with cyclic conformation ( C 2 ), (c) the (FOH) 2 minimum energy complex with linear conformation ( C 1 ) computed at the (A) B3LYP/6-31G(d,p), (B) B3LYP/6-311++G(2d,2p), and (C) MP2/6-311++G(2d,2p) levels. The experimental data are from ref . …”
Section: Resultsmentioning
confidence: 99%
“…For instance, V 3 (F I ,O 2 ) describes the disynaptic attractor of the F 1 −O 2 bond which is numbered as the third one. b From ref .…”
Ab initio calculations have been carried out on dimers of hypofluorous acid(HOF)2. Two stable structures
were found, the first one with an almost linear O···H−O hydrogen bridge and F···H−O hydrogen bond and
the second one being a cyclic dimer with two F···H−O bonds. The most stable complex determined at the
CCSD(T)/6-311++G(2d,2p)//MP2/6-311++G(2d,2p) level is the linear structure, having a stabilization energy
of 2.50 kcal/mol. The cyclic structure is only 0.35 kcal/mol higher in energy than the linear one. The
organization of the attractors achieved by the topological analysis of the electron localization function (ELF)
classifies the interaction in both dimer structures as the unshared-electron type. A transfer of 0.03e between
the HOF monomers in the linear structure is deduced from the comparison of the basin populations. The
integral density over the F−O attractor basins yields 0.32e for the cyclic structure and 0.27 and 0.37 e for the
linear one. The large amount of electron density is concentrated in the regions of the nonbonding valence
pairs. The influence, which a dielectric surrounding has on the HOF dimers, has been investigated with the
SCRF method, with dielectric constants ranging from 2 to 10 at the B3LYP/6-31G(d,p) level. The cyclic
structure which assumed planar (C
2
h
) geometry was found to be unstable (transition state) within a dielectric
medium. The calculated frequencies for the linear complex (C1) agree reasonably well with those observed
in a matrix, particularly in the H−O−F deformation region between 1365−1396 cm-1.
“… 1 Optimized structures of (a) FOH ( C s ), (b) the (FOH) 2 minimum energy complex with cyclic conformation ( C 2 ), (c) the (FOH) 2 minimum energy complex with linear conformation ( C 1 ) computed at the (A) B3LYP/6-31G(d,p), (B) B3LYP/6-311++G(2d,2p), and (C) MP2/6-311++G(2d,2p) levels. The experimental data are from ref . …”
Section: Resultsmentioning
confidence: 99%
“…For instance, V 3 (F I ,O 2 ) describes the disynaptic attractor of the F 1 −O 2 bond which is numbered as the third one. b From ref .…”
Ab initio calculations have been carried out on dimers of hypofluorous acid(HOF)2. Two stable structures
were found, the first one with an almost linear O···H−O hydrogen bridge and F···H−O hydrogen bond and
the second one being a cyclic dimer with two F···H−O bonds. The most stable complex determined at the
CCSD(T)/6-311++G(2d,2p)//MP2/6-311++G(2d,2p) level is the linear structure, having a stabilization energy
of 2.50 kcal/mol. The cyclic structure is only 0.35 kcal/mol higher in energy than the linear one. The
organization of the attractors achieved by the topological analysis of the electron localization function (ELF)
classifies the interaction in both dimer structures as the unshared-electron type. A transfer of 0.03e between
the HOF monomers in the linear structure is deduced from the comparison of the basin populations. The
integral density over the F−O attractor basins yields 0.32e for the cyclic structure and 0.27 and 0.37 e for the
linear one. The large amount of electron density is concentrated in the regions of the nonbonding valence
pairs. The influence, which a dielectric surrounding has on the HOF dimers, has been investigated with the
SCRF method, with dielectric constants ranging from 2 to 10 at the B3LYP/6-31G(d,p) level. The cyclic
structure which assumed planar (C
2
h
) geometry was found to be unstable (transition state) within a dielectric
medium. The calculated frequencies for the linear complex (C1) agree reasonably well with those observed
in a matrix, particularly in the H−O−F deformation region between 1365−1396 cm-1.
“…To the best of our knowledge there are no experimental g factors available for F 2 BOH. In order to get an estimate of the reliability of our predicted values, we have calculated the rotational g tensors in H 2 O, D 2 O, HOF, and F 2 O as selected examples where corresponding experimental data are known [40][41][42][43]. The results obtained with the largest basis set (aug-cc-pVQZ) are given in Table 10 together with the experimental counterparts.…”
“…The quantities averaged over the ground-state function can be further reduced. The first two operators in the average value give ZyLx -LxZy = <*37-^= -ih(Zz) (55) The second term gives ZpyZy -ZyZpy = -ih\Z $-Zy-ZyZ-¿-> = -ih(Z2) (56) dy dy Substituting eq 55 and 56 into eq 54 shows that the Z2 terms cancel, giving…”
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