8,577 research outputs found
Spectroscopic Constants and Vibrational Frequencies for l-C3H+ and Isotopologues from Highly-Accurate Quartic Force Fields: The Detection of l-C3H+ in the Horsehead Nebula PDR Questioned
Very recently, molecular rotational transitions observed in the
photon-dominated region of the Horsehead nebula have been attributed to l-C3H+.
In an effort to corroborate this finding, we employed state-of-the art and
proven high-accuracy quantum chemical techniques to compute spectroscopic
constants for this cation and its isotopologues. Even though the B rotational
constant from the fit of the observed spectrum and our computations agree to
within 20 MHz, a typical level of accuracy, the D rotational constant differs
by more than 40%, while the H rotational constant differs by three orders of
magnitude. With the likely errors in the rotational transition energies
resulting from this difference in D on the order of 1 MHz for the lowest
observed transition (J = 4 <- 3) and growing as J increases, the assignment of
the observed rotational lines from the Horsehead nebula to l-C3H+ is
questionable
The Possible Interstellar Anion CH2CN-: Spectroscopic Constants, Vibrational Frequencies, and Other Considerations
It is hypothesized that the A ^1B_1 <- X ^1A' excitation into the
dipole-bound state of the cyanomethyl anion (CH2CN-) is proposed as the carrier
for one diffuse interstellar band. However, this particular molecular system
has not been detected in the interstellar medium even though the related
cyanomethyl radical and the isoelectronic ketenimine molecule have been found.
In this study we are employing the use of proven quartic force fields and
second-order vibrational perturbation theory to compute accurate spectroscopic
constants and fundamental vibrational frequencies for ^1A' CH2CN- in order to
assist in laboratory studies and astronomical observations
Ab Initio Characterization of Triatomic Bromine Molecules of Potential Interest in Stratospheric Chemistry
The equilibrium structures, harmonic vibrational frequencies, quadratic force fields, dipole moments, and IR intensities of several triatomic bromine compounds of known or potential importance in stratospheric ozone depletion chemistry have been determined using the CCSD(T) electron correlation method in conjunction with a basis set of triple zeta double polarized (TZ2P) quality. Specifically, the molecules included in the present study are HOBr, HBrO, FOBr, FBrO, BrNO, BrON, Br2O, BrBrO, BrCN, BrNC, ClOBr, ClBrO, and BrClO. Very accurate isomeric energy differences have also been determined at the CCSD(T) level with atomic natural orbital basis sets that include through g-type functions. In most cases, the isomer with a normal neutral Lewis dot structure is the lowest energy form, with the single exception that FBRO is predicted to be 11.1 kcal/mol (0 K) lower in energy than FOBr. In all cases, however, the hypervalent isomer is more stable relative to the isomer with a normal Lewis dot structure as compared to the chlorine analogs. Consistent with this observation, the energy of the last three molecules given above increases in the order ClOBr less than ClBrO less than BrClO. The CCSD(T)/TZ2P geometries and vibrational frequencies are in good agreement with the available experimental data. Heats of formation are determined for all species using a combination of theoretical isomeric, homodesmic, and isodesmic reaction energies. The accuracy of these quantities is ultimately dependent on the reliability of the experimental heat of formation of HOBr
The Failure of Correlation to Describe Out-of-Plane Carbon=Carbon Bending
Carbon-carbon multiply bonded systems are improperly described with standard correlation methods and basis sets. For computations of vibrational modes, the out-of- plane bends can be reported as imaginary at worst or simply too low at best. Utilizing the simplest of aromatic structures (cyclopropenylidene) and various levels of theory, this work diagnoses this known behavior for the first time. A combined 1-particle and n-particle basis set effect conspire to produce these non-physical results. When moving from sp2 to sp3 hybridization in the carbon atoms, the larger number of basis functions overcorrects the energy. This is exacerbated by correlation methods. These allow for occupation of the and orbitals in the expanded wave function that combine with the hydrogen s orbitals. As a result, the improperly described space can be further and non-physically stabilized by post-Hartree-Fock correlation. This represents a fundamental problem with at least Hartree-Fock based methods of all flavors in describing carbon. Beyond being a flaw in quantum chemical theory, other repercussions will be present in computations regarding spectroscopy as well as energy and environmental studies where highly-accurate hydrocabon vibrational transitions or thermochemical data are needed
Accurate ab initio anharmonic force field and heat of formation for silane, SiH_4
From large basis set coupled cluster calculations and a minor empirical
adjustment, an anharmonic force field for silane has been derived that is
consistently of spectroscopic quality ( on vibrational
fundamentals) for all isotopomers of silane studied. Inner-shell polarization
functions have an appreciable effect on computed properties and even on
anharmonic corrections. From large basis set coupled cluster calculations and
extrapolations to the infinite-basis set limit, we obtain TAE_0=303.80 \pm 0.18
kcal/mol, which includes an anharmonic zero-point energy (19.59 kcal/mol),
inner-shell correlation (-0.36 kcal/mol), scalar relativistic corrections
(-0.70 kcal/mol), and atomic spin-orbit corrections (-0.43 kcal/mol). In
combination with the recently revised \HVSI{0}, we obtain , in between the two established
experimental values.Comment: Mol. Phys., in pres
The structures, binding energies and vibrational frequencies of Ca3 and Ca4: An application of the CCSD(T) method
The Ca3 and Ca4 metallic clusters have been investigated using state-of-the-art ab initio quantum mechanical methods. Large atomic natural orbital basis sets have been used in conjunction with the singles and doubles coupled-cluster (CCSD) method, a coupled-cluster method that includes a perturbational estimate of connected triple excitations, denoted CCSD(T), and the multireference configuration interaction (MRCI) method. The equilibrium geometries, binding energies and harmonic vibrational frequencies have been determined with each of the methods so that the accuracy of the coupled-cluster methods may be assessed. Since the CCSD(T) method reproduces the MRCI results very well, cubic and quartic force fields of Ca3 and Ca4 have been determined using this approach and used to evaluate the fundamental vibrational frequencies. The infrared intensities of both the e' mode of Ca3 and the t2 mode of Ca4 are found to be small. The results obtained in this study are compared and contrasted with those from our earlier studies on small Be and Mg clusters
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