Search results for "Bond length"
showing 10 items of 209 documents
Photochemical ligand rearrangement in dirhodium(II) compounds. Structure of Rh2(O2CCH3)2(η2-O2CCH3)[(C6H4)PPh2] (η2-PCCl)(PCClP-ClC6H4)Ph2
1995
Abstract The photochemical reaction of the adducts Rh2(O2CCH3)3[(C6H4)P(o-ClC6H4)Ph]· (P(p-XC6H4)3) (X=H, Me, Cl), yield the compounds Rh2(O2CCH3)2(η2-O2CCH3)[(p-XC6H3)P (p-XC6H4)2](η2-PCCl), (PCCl=P(o-ClC6H4)Ph2) in a ligand rearrangement reaction that involves activation of CH and RhC bonds. The factors that favour this process are studied by carrying out photochemical reactions with different phosphines. The structures of Rh2(O2CCH3)2(η2-O2CCH3) [(C6H4)PPh2](η2-PCCl) has been determined by X-ray diffraction. Mr=1321.1, orthorhombic, space group Pbcn, a=20.339(8), b=20.07(6), c=23.07(3) A , V=9413(3) A 3 , Z=8, D x =1.86 g cm −3 . Mo Kα radiation (graphite crystal monochromator, λ=0.071…
The chemical bonds in CuH, Cu2, NiH, and Ni2 studied with multiconfigurational second order perturbation theory
1994
The performance of multiconfigurational second order perturbation theory has been analyzed for the description of the bonding in CuH, Cu2, NiH, and Ni2. Large basis sets based on atomic natural orbitals (ANOS) were employed. The effects of enlarging the active space and including the core‐valence correlation contributions have also been analyzed. Spectroscopic constants have been computed for the corresponding ground state. The Ni2 molecule has been found to have a 0+g ground state with a computed dissociation energy of 2.10 eV, exp. 2.09 eV, and a bond distance of 2.23 Å. The dipole moments of NiH and CuH are computed to be 2.34 (exp. 2.4±0.1) and 2.66 D, respectively. pou@uv.es ; merchan@…
Experimental and quantum-chemical characterization of heavy carbon subchalcogenides: Infrared detection of SeC3Se
2021
Abstract High-resolution infrared studies of laser ablation products from carbon-selenium targets have revealed a new vibrational band at 2057 cm−1 that is identified as the ν 3 vibrational fundamental of the SeC3Se cluster. Because of the rich isotopic composition of selenium and the heavy nuclear masses involved, the vibrational band shows a relatively compact and complex structure despite the simple linear geometric arrangement. Overall, rotational-vibrational lines of six isotopologues could be assigned and fitted permitting the derivation of an accurate selenium-carbon bond length. Spectroscopic analysis has been greatly supported by high-level quantum-chemical calculations of the mol…
DFT calculation of structures and NMR chemical shifts of simple models of small diameter zigzag single wall carbon nanotubes (SWCNTs)
2011
Linearly conjugated benzene rings (acenes), belt-shape molecules (cyclic acenes) and model single wall carbon nanotubes (SWCNTs) were fully optimized at the unrestricted level of density functional theory (UB3LYP/6-31G*). The models of SWCNTs were selected to get some insight into the potential changes of NMR chemical shift upon systematic increase of the molecular size. The theoretical NMR chemical shifts were calculated at the B3LYP/pcS-2 level of theory using benzene as reference. In addition, the change of radial breathing mode (RBM), empirically correlated with SWCNT diameter, was directly related with the radius of cyclic acenes. Both geometrical and NMR parameters were extrapolated t…
On the approximation of the similarity-transformed Hamiltonian in single-reference and multireference coupled cluster theory
2012
Abstract We consider the recursive single commutator (RSC) approximation of the Baker–Campbell–Hausdorff expansion introduced by Yanai and Chan [T. Yanai, G.K.-L. Chan, J. Chem. Phys. 124 (2006) 194106] and apply it in order to approximate the similarity transformation of the Hamiltonian in both traditional and unitary coupled cluster theory. The equilibrium bond distance, harmonic vibrational frequency, and anharmonic constant of H2, HF, N2, CuH, and Cu2 were computed using the coupled cluster approach with single and double excitations (CCSD) and CCSD with the RSC approximation of the similarity-transformed Hamiltonian (CCSD-RSC). Our results demonstrate that the RSC approximation introdu…
Full configuration interaction calculation of BeH adiabatic states.
2008
An all-electron full configuration interaction (FCI) calculation of the adiabatic potential energy curves of some of the lower states of BeH molecule is presented. A moderately large ANO basis set of atomic natural orbitals (ANO) augmented with Rydberg functions has been used in order to describe the valence and Rydberg states and their interactions. The Rydberg set of ANOs has been placed on the Be at all bond distances. So, the basis set can be described as 4s3p2d1f3s2p1d(BeH)+4s4p2d(Be). The dipole moments of several states and transition dipole strengths from the ground state are also reported as a function of the R(Be-H) distance. The position and the number of states involved in sever…
On a topological interpretation of electronic and vibrational molecular energies
1998
Abstract A relationship between Randic's connectivity index and various quantum mechanical parameters derived from the Huckel Molecular Orbital (HMO) approach is demonstrated. When applied to conjugated hydrocarbons, this index represents the measure of the global π electron molecular energy and, therefore, of the resonance energy. Moreover, the development of the procedure, allows the introduction of a new definition of the bond order which, in turn, makes possible a better prediction not only for bond lengths of naphtalene but also for the resonance integral and conjugation energy for butadiene. Also, a corrected value for the Randic index is deduced, which allows for the reduction of the…
Theoretical spectroscopic parameters of the alkali monofluorides LiF, NaF and KF
1992
Abstract Multireference configuration interaction and second-order perturbation theory are used to determine accurate spectroscopic parameters for the ground state of the alkali monofluorides from LiF to KF. Systematic saturation of the spdf subspaces of the atomic basis sets for the electron affinity of fluorine and the ionization potential of the metals have been shown to be more efficient than for the approximate dissociation energies in the molecule. the calculated rotational and vibrational constants and transitions for the three systems show excellent agreement with the expeirmental data.
Crystal structure and IR spectrum of 1-O-α-d-glucopyranosyl-d-mannitol–ethanol (2/1)
1999
Abstract 1- O - α - d -Glucopyranosyl- d -mannitol–ethanol (2/1), (C 12 H 24 O 11 ) 2 –C 2 H 5 OH, crystallizes in the monoclinic space group P2 1 with unit cell dimensions a =11.4230(8) A, b =9.525(4) A, c =15.854(2) A, β =102.751(7)° and V =1682.4(7) A 3 , Z =2, D x =1.45 Mg m −3 , λ (Mo-K α )=0.71069 A, μ=0.128 mm −1 , F (000)=788 and T =293(2) K. The structure was solved by direct methods and refined by least-squares calculations on F 2 to R 1 =0.0371[ I >2 σ ( I )], and 0.0930 (all data, 3542 independent reflections, R int =0.021). There are two molecules of glucopyranosylmannitol (GPM) and one ethanol molecule in the asymmetric unit, and the glucopyranosyl ring adopts a chair conforma…
N-Methyl-3-methylsulfonyl-N-nitroaniline
2005
In the title compound, C8H10N2O4S, the N—N bond length [1.3488 (18) A] indicates some double-bond character, while the torsion angle between the aromatic ring and the nitramine group [66.3 (2)°] rules out further delocalization in the molecule. The geometry of the methylsulfonyl substituent is quasi-tetrahedral, as expected. The crystal packing is stabilized by C—H⋯O hydrogen bonds, with the molecules arranged in chains extended along the [101] direction.