Theoretical investigation on the protonation reactions and products of the stable [N,C,C,S] isomers

A theoretical study on the protonation system of [N,C,C,S], [H,N,C,C,S]+, was performed at the B3LYP/6‐311++G(d,p) and CCSD(T)/6‐311++G(2df,2p) (single point) levels of theory. On the doublet [H,N,C,C,S]+ surface, 24 species were located as energy minima and 10 of them were considered as kinetically stable species. The species HNCCS+ with 2A′ state and a shallow W‐shaped skeleton was predicted to be the global minimum and kinetically the most stable species, being in good agreement with previous experimental findings. Furthermore, the protonation reactions of the stable [N,C,C,S] isomers were investigated in detail. The calculation results indicated that the [N,C,C,S] isomers may be significantly stabilized upon protonation. Finally, the possible covalent structures of the [H,N,C,C,S]+ isomers with considerable stability were briefly discussed. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007

[1]  Y. Hirahara,et al.  Pulsed‐discharge‐nozzle Fourier‐transform microwave spectroscopy of HC3S(2Πr) and HC4S(2Πi) , 1994 .

[2]  G. Winnewisser,et al.  Rotational spectra of C4N, C6N, and the isotopic species of C3N , 2003 .

[3]  Y. Endo,et al.  Laser induced fluorescence spectroscopy of the HC4S and DC4S radicals , 2002 .

[4]  P. Thaddeus,et al.  Carbon chains and rings in the laboratory and in space. , 2001, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[5]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[6]  Krishnan Raghavachari,et al.  Gaussian-2 theory for molecular energies of first- and second-row compounds , 1991 .

[7]  Y. Endo,et al.  Laser induced fluorescence spectroscopy of the HC6S radical , 2002 .

[8]  Yi‐hong Ding,et al.  Theoretical study on structures and stability of C4P isomers. , 2006, The journal of physical chemistry. A.

[9]  Y. Kasai,et al.  Laboratory detection of C5S by pulsed-discharge-nozzle Fourier transform microwave spectroscopy , 1993 .

[10]  K. Shibuya,et al.  Laser induced fluorescence of NCS in the gas phase , 1984 .

[11]  Michael J. Frisch,et al.  Semi-direct algorithms for the MP2 energy and gradient , 1990 .

[12]  David Smith.  THE ION CHEMISTRY OF INTERSTELLAR CLOUDS , 1992 .

[13]  P. Feldman,et al.  C3S and C5S in IRC +10216 , 1993 .

[14]  E. Ferguson,et al.  Experimental study of HCN+ and HNC+ ion chemistry , 1990 .

[15]  H. Bernhard Schlegel,et al.  Reaction Path Following in Mass-Weighted Internal Coordinates , 1990 .

[16]  J. Pople,et al.  Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions , 1980 .

[17]  E. Gottlieb,et al.  A millimeter-wave study and astronomical search for the HCCCS radical , 1994 .

[18]  B. Schmitt,et al.  Plausible condensates in Titan’s stratosphere from Voyager infrared spectra , 1999 .

[19]  Y. Hirahara,et al.  Laboratory detection of a new free radical C4S (3Sigma , 1993 .

[20]  Michael J. Frisch,et al.  A direct MP2 gradient method , 1990 .

[21]  T. Kolev,et al.  Vibrational assignment of para-dimethylaminobenzil and its 18O-substituted derivative , 1997 .

[22]  Krishnan Raghavachari,et al.  Gaussian-2 theory using reduced Moller--Plesset orders , 1993 .

[23]  E. P. Hunter,et al.  Evaluated Gas Phase Basicities and Proton Affinities of Molecules: An Update , 1998 .

[24]  Y. Ohshima,et al.  ROTATIONAL SPECTRA AND STRUCTURES OF CARBON MONOXIDES C5O, C7O, AND C9O , 1995 .

[25]  Patrick Thaddeus,et al.  Laboratory measurement of the rotational spectrum of SiCC , 1989 .

[26]  A. Murakami.  A quantum chemical study on the linear C2S and C3S molecules , 1990 .

[27]  L. Radom,et al.  Proton-Transport Catalysis: A Systematic Study of the Rearrangement of the Isoformyl Cation to the Formyl Cation , 1997 .

[28]  D. W. Clarke,et al.  Titan haze: structure and properties of cyanoacetylene and cyanoacetylene-acetylene photopolymers. , 1997, Icarus.

[29]  M. Head‐Gordon,et al.  Fifth order Moeller-Plesset perturbation theory: comparison of existing correlation methods and implementation of new methods correct to fifth order , 1990 .

[30]  M. Horn,et al.  Structure of the CCCN and CCCCH radicals: Isotopic substitution and ab initio theory , 1995 .

[31]  A. D. McLean,et al.  Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z=11–18 , 1980 .

[32]  S. Laurent,et al.  Iminoethenethiones, Rn=c=c=s - Characterization by Neutralization-Reionization Mass-Spectrometry and G2(Mp2) Theory , 1994 .

[33]  R. Dixon,et al.  Emission and Absorption Spectra of NCO and NCS , 1958, Nature.

[34]  Y. Endo,et al.  Pure rotational spectrum of the NCCS radical studied by Fourier-transform microwave spectroscopy , 2003 .

[35]  Axel D. Becke,et al.  Density-functional thermochemistry. I. The effect of the exchange-only gradient correction , 1992 .

[36]  W. Irvine.  Organic molecules in the gas phase of dense interstellar clouds. , 1995, Advances in space research : the official journal of the Committee on Space Research.

[37]  Curtis L. Janssen,et al.  An efficient reformulation of the closed‐shell coupled cluster single and double excitation (CCSD) equations , 1988 .

[38]  J. S. Francisco,et al.  Determination of the heats of formation of CCCN and HCCCN , 1994 .

[39]  G. Scuseria,et al.  Is coupled cluster singles and doubles (CCSD) more computationally intensive than quadratic configuration interaction (QCISD) , 1989 .

[40]  Yuan-Pern Lee,et al.  Laboratory investigation on the formation of unsaturated nitriles in Titan's atmosphere via reactions of CN radicals with unsaturated hydrocarbons as studied in crossed molecular beams experiments , 1999 .

[41]  Y. Kasai,et al.  Laboratory Detection of the C5N Radical by Fourier Transform Microwave Spectroscopy , 1997 .

[42]  H. Kohguchi,et al.  Pulsed‐discharge nozzle Fourier‐transform microwave spectroscopy of the HC4O radical , 1994 .

[43]  Michael J. Frisch,et al.  MP2 energy evaluation by direct methods , 1988 .

[44]  T. Amano.  Millimeter‐wave spectrum of NCS radical in the ground 2Π state , 1991 .

[45]  F. J. Northrup,et al.  Laser‐induced fluorescence spectroscopy of NCS in a free jet expansion , 1989 .

[46]  A. D. McLean,et al.  Is interstellar detection of higher members of the linear radicals CnCH and CnN feasible? , 1991, The Astrophysical journal.

[47]  A. Becke.  Density-functional thermochemistry. II: The effect of the Perdew-Wang generalized-gradient correlation correction , 1992 .

[48]  H. Bernhard Schlegel,et al.  An improved algorithm for reaction path following , 1989 .

[49]  M. Plesset,et al.  Note on an Approximation Treatment for Many-Electron Systems , 1934 .

[50]  Y. Ohshima,et al.  Fourier‐transform microwave spectroscopy of triplet carbon monoxides, C2O, C4O, C6O, and C8O , 1995 .

[51]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[52]  L. Bizzocchi,et al.  Millimeter-wave spectroscopy and coupled cluster calculations for NCCP , 2000 .

[53]  M. Horn,et al.  Ab initio calculations on molecules of interest to interstellar cloud chemistry , 1993 .

[54]  C. McKay,et al.  Transition from gaseous compounds to aerosols in Titan's atmosphere , 2002 .

[55]  D. Bohme.  Proton transport in the catalyzed gas-phase isomerization of protonated molecules , 1992 .

[56]  R. Dixon,et al.  Electronic absorption spectrum of the NCS free radical , 1968 .