Ab initio characterization of XH3 (X = N,P). Part II. Electric, magnetic and spectroscopic properties of ammonia and phosphine

  title={Ab initio characterization of XH3 (X = N,P). Part II. Electric, magnetic and spectroscopic properties of ammonia and phosphine},
  author={Cristina Puzzarini},
  journal={Theoretical Chemistry Accounts},
  • C. Puzzarini
  • Published 29 January 2008
  • Chemistry, Physics
  • Theoretical Chemistry Accounts
The coupled cluster theory in conjunction with core valence triple and quadruple zeta basis sets has been employed for investigating electric, magnetic and spectroscopic properties of ammonia and phosphine. Namely molecular dipole and quadrupole moments, NMR shielding and spin-rotation constants, as well as spectroscopic properties such as rotational and centrifugal distortion constants as well as harmonic and anharmonic frequencies of NH3 and PH3 have been determined at a high level of… 

Ab initio studies of the structure and spectroscopy of CHNMg stoichiometry molecules and van der Waals complexes.

A high-level ab initio study was conducted over the range of tetraatomic molecules containing H, C, N, and Mg, leading to the optimization of their geometry in the lowest singlet and triplet excited states.

Nuclear quadrupole coupling constants for N2O: experiment and theory.

Ab initio computations for the linear FH···N(2)O complex confirm the large change in EFGs imposed by a single perturber and demonstrate that only CCSD(T) and MRCI methods are capable of accurately predicting the NQCCs of the central and terminal nitrogen atoms.

NMR shielding constants in PH3, absolute shielding scale, and the nuclear magnetic moment of 31P.

Analysis of the relativistic corrections to nuclear magnetic resonance (NMR) shielding constants is analyzed, comparing the constants computed using the four-component Dirac-Hartree-Fock approach, theFour-component density functional theory (DFT), and the Breit-Pauli perturbation theory (BPPT) with nonrelativistic Hartree-fock or DFT reference functions.

What are the spectroscopic properties of HFC-32? Answers from DFT

Although coupled cluster theory coupled to large basis sets can reach impressive accuracies for thermochemical and spectroscopic properties, it is still limited to small/medium sized molecules.

Accurate molecular structure and spectroscopic properties of nucleobases: a combined computational-microwave investigation of 2-thiouracil as a case study.

The computational composite scheme purposely set up for accurately describing the electronic structure and spectroscopic properties of small biomolecules has been applied to the first study of the

Temperature-dependent, effective structures of the 14NH3 and 14ND3 molecules.

Structural parameters confirm the less accurate results of a room-temperature gas-electron-diffraction study on the basis of the difference in the r(g,T)(NH) bond lengths of the two spin isomers of (14)NH(3) is 3 × 10(-5) Å at 0 K, the difference diminishes at temperatures of about 30-50 K.

Towards the versatile DFT and MP2 computational schemes for 31P NMR chemical shifts taking into account relativistic corrections

The GIAO‐DFT‐KT2/pcS‐3//PCS‐2 scheme with relativistic corrections and solvent effects taken into account is recommended as the most versatile computational scheme for the calculation of 31P NMR chemical shifts characterized by a mean absolute error of ca 9 ppm in the range of 550‬ppm.

Nuclear spin conversion in H 2 O

Nuclear spin conversion (NSC) in water molecules has often been investigated in the gas or solid phase. It has not been observed in the former yet because of the difficulty in producing an efficient

How accurate are static polarizability predictions from density functional theory? An assessment over 132 species at equilibrium geometry.

A database of benchmark static polarizabilities for 132 small species at equilibrium geometry is developed, using coupled cluster theory through triple excitations (extrapolated to the complete basis set limit), for the purpose of developing and assessing density functionals.



An ab initio study of vibrational corrections to the electrical properties of the second-row hydrides

Accurate ab initio calculations of the dipole and quadrupole moments, polarizabilities and polarizability anisotropies are reported for the second-row hydrides, silane (SiH4), phosphine (PH3),

The nuclear-spin-rotation constants of HCY, HSiY, and SiY(2) (Y=F, Cl): an ab initio study.

The nuclear-spin-rotation constants of fluoro- (HCF) and chloro- (HCCl) carbene, of the corresponding silylenes (HSiF and HSiCl), and of difluoro- and dichlorosilylene (SiF(2) and SiCl(2)) are