Correlation consistent basis sets for explicitly correlated wavefunctions: pseudopotential-based basis sets for the post-d main group elements Ga-Rn.

New correlation consistent basis sets, cc-pVnZ-PP-F12 (n = D, T, Q), for all the post-d main group elements Ga-Rn have been optimized for use in explicitly correlated F12 calculations. The new sets, which include not only orbital basis sets but also the matching auxiliary sets required for density fitting both conventional and F12 integrals, are designed for correlation of valence sp, as well as the outer-core d electrons. The basis sets are constructed for use with the previously published small-core relativistic pseudopotentials of the Stuttgart-Cologne variety. Benchmark explicitly correlated coupled-cluster singles and doubles with perturbative triples [CCSD(T)-F12b] calculations of the spectroscopic properties of numerous diatomic molecules involving 4p, 5p, and 6p elements have been carried out and compared to the analogous conventional CCSD(T) results. In general the F12 results obtained with a n-zeta F12 basis set were comparable to conventional aug-cc-pVxZ-PP or aug-cc-pwCVxZ-PP basis set calculations obtained with x = n + 1 or even x = n + 2. The new sets used in CCSD(T)-F12b calculations are particularly efficient at accurately recovering the large correlation effects of the outer-core d electrons.

[1]  Christof Hättig,et al.  Explicitly correlated electrons in molecules. , 2012, Chemical reviews.

[2]  Trygve Helgaker,et al.  Basis-set convergence in correlated calculations on Ne, N2, and H2O , 1998 .

[3]  Werner Kutzelnigg,et al.  r12-Dependent terms in the wave function as closed sums of partial wave amplitudes for large l , 1985 .

[4]  Kirk A Peterson,et al.  Molecular core-valence correlation effects involving the post-d elements Ga-Rn: benchmarks and new pseudopotential-based correlation consistent basis sets. , 2010, The Journal of chemical physics.

[5]  Frank Jensen,et al.  Atomic orbital basis sets , 2013 .

[6]  T. H. Dunning.  Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen , 1989 .

[7]  S. F. Boys,et al.  The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors , 1970 .

[8]  Frederick R. Manby,et al.  Explicitly correlated coupled cluster methods with pair-specific geminals , 2011 .

[9]  Angela K. Wilson,et al.  Gaussian basis sets for use in correlated molecular calculations. VII. Valence, core-valence, and scalar relativistic basis sets for Li, Be, Na, and Mg , 2011 .

[10]  Toru Shiozaki,et al.  Explicitly correlated multireference configuration interaction: MRCI-F12. , 2011, The Journal of chemical physics.

[11]  Christof Hättig,et al.  CC2 excitation energy calculations on large molecules using the resolution of the identity approximation , 2000 .

[12]  K. Peterson,et al.  Correlation consistent, Douglas–Kroll–Hess relativistic basis sets for the 5p and 6p elements , 2014, Theoretical Chemistry Accounts.

[13]  Florian Weigend,et al.  Hartree–Fock exchange fitting basis sets for H to Rn † , 2008, J. Comput. Chem..

[14]  Hans-Joachim Werner,et al.  Extrapolating MP2 and CCSD explicitly correlated correlation energies to the complete basis set limit with first and second row correlation consistent basis sets. , 2009, The Journal of chemical physics.

[15]  Hans-Joachim Werner,et al.  Systematically convergent basis sets for explicitly correlated wavefunctions: the atoms H, He, B-Ne, and Al-Ar. , 2008, The Journal of chemical physics.

[16]  Gustavo E. Scuseria,et al.  The open-shell restricted Hartree—Fock singles and doubles coupled-cluster method including triple excitations CCSD (T): application to C+3 , 1991 .

[17]  Kirk A. Peterson,et al.  Optimized complementary auxiliary basis sets for explicitly correlated methods: aug-cc-pVnZ orbital basis sets , 2009 .

[18]  Wenjian Liu,et al.  A small-core multiconfiguration Dirac–Hartree–Fock-adjusted pseudopotential for Tl – application to TlX (X = F, Cl, Br, I) , 2000 .

[19]  Hans-Joachim Werner,et al.  Simplified CCSD(T)-F12 methods: theory and benchmarks. , 2009, The Journal of chemical physics.

[20]  Florian Weigend,et al.  A fully direct RI-HF algorithm: Implementation, optimised auxiliary basis sets, demonstration of accuracy and efficiency , 2002 .

[21]  Toru Shiozaki,et al.  Communication: Second-order multireference perturbation theory with explicit correlation: CASPT2-F12. , 2010, The Journal of chemical physics.

[22]  Trygve Helgaker,et al.  Basis-set convergence of correlated calculations on water , 1997 .

[23]  David Feller,et al.  On the effectiveness of CCSD(T) complete basis set extrapolations for atomization energies. , 2011, The Journal of chemical physics.

[24]  Christof Hättig,et al.  Optimization of auxiliary basis sets for RI-MP2 and RI-CC2 calculations: Core–valence and quintuple-ζ basis sets for H to Ar and QZVPP basis sets for Li to Kr , 2005 .

[25]  B. Shepler,et al.  On the spectroscopic and thermochemical properties of ClO, BrO, IO, and their anions. , 2006, The journal of physical chemistry. A.

[26]  Kirk A Peterson,et al.  Optimized auxiliary basis sets for explicitly correlated methods. , 2008, The Journal of chemical physics.

[27]  Christof Hättig,et al.  Explicitly Correlated Coupled-Cluster Theory , 2010 .

[28]  Edward F. Valeev.  Improving on the resolution of the identity in linear R12 ab initio theories , 2004 .

[29]  K. Peterson.  Systematically convergent basis sets with relativistic pseudopotentials. I. Correlation consistent basis sets for the post-d group 13–15 elements , 2003 .

[30]  Michael Dolg,et al.  Small-core multiconfiguration-Dirac–Hartree–Fock-adjusted pseudopotentials for post-d main group elements: Application to PbH and PbO , 2000 .

[31]  Angela K. Wilson,et al.  Gaussian basis sets for use in correlated molecular calculations. X. The atoms aluminum through argon revisited , 2001 .

[32]  Hans-Joachim Werner,et al.  Coupled cluster theory for high spin, open shell reference wave functions , 1993 .

[33]  Hans-Joachim Werner,et al.  Application of explicitly correlated coupled-cluster methods to molecules containing post-3d main group elements , 2011 .

[34]  J. Grant Hill,et al.  Auxiliary basis sets for density‐fitting second‐order Møller–Plesset perturbation theory: Weighted core‐valence correlation consistent basis sets for the 4d elements Y–Pd , 2013, J. Comput. Chem..

[35]  H. Stoll,et al.  Systematically convergent basis sets with relativistic pseudopotentials. II. Small-core pseudopotentials and correlation consistent basis sets for the post-d group 16–18 elements , 2003 .

[36]  Frederick R Manby,et al.  General orbital invariant MP2-F12 theory. , 2007, The Journal of chemical physics.

[37]  Nathan J. DeYonker,et al.  Systematically convergent correlation consistent basis sets for molecular core-valence correlation effects: the third-row atoms gallium through krypton. , 2007, The journal of physical chemistry. A.

[38]  J Grant Hill,et al.  Correlation consistent basis sets for explicitly correlated wavefunctions: valence and core-valence basis sets for Li, Be, Na, and Mg. , 2010, Physical chemistry chemical physics : PCCP.

[39]  F. Weigend,et al.  Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. , 2005, Physical chemistry chemical physics : PCCP.

[40]  F. Manby,et al.  Efficient Explicitly Correlated Coupled-Cluster Approximations , 2010 .

[41]  Trygve Helgaker,et al.  Quantitative quantum chemistry , 2008 .

[42]  Angela K. Wilson,et al.  Gaussian basis sets for use in correlated molecular calculations. IX. The atoms gallium through krypton , 1993 .

[43]  J. Grant Hill,et al.  Gaussian basis sets for molecular applications , 2013 .

[44]  D. Schwenke.  The extrapolation of one-electron basis sets in electronic structure calculations: how it should work and how it can be made to work. , 2005, The Journal of chemical physics.

[45]  Edward F. Valeev,et al.  Explicitly correlated R12/F12 methods for electronic structure. , 2012, Chemical reviews.

[46]  J Grant Hill,et al.  Correlation consistent basis sets for molecular core-valence effects with explicitly correlated wave functions: the atoms B-Ne and Al-Ar. , 2010, The Journal of chemical physics.

[47]  Christof Hättig,et al.  Geometry optimizations with the coupled-cluster model CC2 using the resolution-of-the-identity approximation , 2003 .

[48]  Holger Patzelt,et al.  RI-MP2: optimized auxiliary basis sets and demonstration of efficiency , 1998 .

[49]  T. Dunning,et al.  Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions , 1992 .