The electronic circular dichroism of nicotine in aqueous solution: a test case for continuum and mixed explicit-continuum solvation approaches.

In this paper, we extend an integrated QM/MM/polarizable continuum model (PCM) method, which combines a fluctuating charge (FQ) approach to the MM polarization with the PCM, to describe electronic circular dichroism (ECD) spectra of systems in aqueous solution. The main features of the approach are presented, and then applications to the UV and ECD spectra of neutral (S)-nicotine in aqueous solution are reported. The performance of the QM/FQ/PCM is compared with that of the PCM against newly measured UV ECD spectra, which are in agreement with previous findings. The inclusion of specific solvation effects via the QM/FQ/PCM method leads to an improvement in the calculated spectra compared to the experimental findings, though the pure PCM results are still qualitatively correct and are a useful tool for the characterization of the states.

[1]  P. Wipf,et al.  Contribution of a solute's chiral solvent imprint to optical rotation. , 2007, Angewandte Chemie.

[2]  N. Handy,et al.  A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP) , 2004 .

[3]  Steven J. Stuart,et al.  Dynamical fluctuating charge force fields: Application to liquid water , 1994 .

[4]  Benedetta Mennucci,et al.  A TDDFT/MMPol/PCM model for the simulation of exciton-coupled circular dichroism spectra. , 2014, Physical chemistry chemical physics : PCCP.

[5]  T. Crawford,et al.  Large solvation effect in the optical rotatory dispersion of norbornenone. , 2014, Angewandte Chemie.

[6]  Vincenzo Barone,et al.  A gauge invariant multiscale approach to magnetic spectroscopies in condensed phase: general three-layer model, computational implementation and pilot applications. , 2013, The Journal of chemical physics.

[7]  T Daniel Crawford,et al.  Coupled cluster calculations of optical rotatory dispersion of (S)-methyloxirane. , 2004, The Journal of chemical physics.

[8]  S. Monti,et al.  Environmental effects on the spectroscopic properties of gallic acid: a combined classical and quantum mechanical study. , 2005, The journal of physical chemistry. A.

[9]  K. Ruud,et al.  Solvent effects on zero-point vibrational corrections to optical rotations and nuclear magnetic resonance shielding constants , 2008 .

[10]  V. Barone,et al.  Toward an Accurate Modeling of Optical Rotation for Solvated Systems: Anharmonic Vibrational Contributions Coupled to the Polarizable Continuum Model. , 2012, Journal of chemical theory and computation.

[11]  Pilar Gema Rodríguez Ortega,et al.  Vibrational circular dichroism and theoretical study of the conformational equilibrium in (-)-S-nicotine. , 2015, Chemphyschem : a European journal of chemical physics and physical chemistry.

[12]  J. Autschbach,et al.  Time-dependent density functional response theory for electronic chiroptical properties of chiral molecules. , 2011, Topics in current chemistry.

[13]  C. Vega,et al.  A general purpose model for the condensed phases of water: TIP4P/2005. , 2005, The Journal of chemical physics.

[14]  V. Barone,et al.  Development of a virtual spectrometer for chiroptical spectroscopies: the case of nicotine. , 2013, Chirality.

[15]  W. Goddard,et al.  Charge equilibration for molecular dynamics simulations , 1991 .

[16]  F. Lipparini,et al.  The Optical Rotation of Methyloxirane in Aqueous Solution: A Never Ending Story? , 2013, Journal of chemical theory and computation.

[17]  Junmei Wang,et al.  Development and testing of a general amber force field , 2004, J. Comput. Chem..

[18]  Vincenzo Barone,et al.  Polarizable Force Fields and Polarizable Continuum Model: A Fluctuating Charges/PCM Approach. 1. Theory and Implementation. , 2011, Journal of chemical theory and computation.

[19]  Peter A. Kollman,et al.  Application of the multimolecule and multiconformational RESP methodology to biopolymers: Charge derivation for DNA, RNA, and proteins , 1995, J. Comput. Chem..

[20]  P. Bouř,et al.  Explicit versus implicit solvent modeling of Raman optical activity spectra. , 2011, The journal of physical chemistry. B.

[21]  B. Mennucci,et al.  Modeling the solvation of peptides. The case of (s)-N-acetylproline amide in liquid water. , 2008, The journal of physical chemistry. B.

[22]  Benedetta Mennucci,et al.  Continuum Solvation Models: What Else Can We Learn from Them? , 2010 .

[23]  K. Wiberg,et al.  Conformational effects on optical rotation. 3-substituted 1-butenes. , 2003, Journal of the American Chemical Society.

[24]  K. Mikkelsen,et al.  Coupled cluster and density functional theory studies of the vibrational contribution to the optical rotation of (S)-propylene oxide. , 2006, Journal of the American Chemical Society.

[25]  Jacopo Tomasi,et al.  Vibrational circular dichroism within the polarizable continuum model: a theoretical evidence of conformation effects and hydrogen bonding for (S)-(-)-3-butyn-2-ol in CCl4 solution , 2002 .

[26]  Peter M. Kasson,et al.  GROMACS 4.5: a high-throughput and highly parallel open source molecular simulation toolkit , 2013, Bioinform..

[27]  J. Neugebauer.  Induced chirality in achiral media-how theory unravels mysterious solvent effects. , 2007, Angewandte Chemie.

[28]  Giovanni Scalmani,et al.  Analytical First and Second Derivatives for a Fully Polarizable QM/Classical Hamiltonian. , 2012, Journal of chemical theory and computation.

[29]  F. Lipparini,et al.  Vertical Electronic Excitations in Solution with the EOM-CCSD Method Combined with a Polarizable Explicit/Implicit Solvent Model. , 2013, Journal of chemical theory and computation.

[30]  N. Berova,et al.  Applications in stereochemical analysis of synthetic compounds, natural products, and biomolecules , 2012 .

[31]  Kevin McAdam,et al.  Spectroscopic Studies on Nicotine and Nornicotine in the UV Region† , 2013, Chirality.

[32]  S. Zilberg,et al.  The electronic origin of the dual fluorescence in donor-acceptor substituted benzene derivatives. , 2006, Journal of the American Chemical Society.

[33]  K. Ruud,et al.  The importance of molecular vibrations: the sign change of the optical rotation of methyloxirane. , 2005, Angewandte Chemie.

[34]  J. Autschbach,et al.  A pragmatic recipe for the treatment of hindered rotations in the vibrational averaging of molecular properties. , 2008, Chemphyschem : a European journal of chemical physics and physical chemistry.

[35]  F. Melendez,et al.  Analysis of B3LYP and MP2 conformational population distributions in trans‐nicotine, acetylcholine, and ABT‐594 , 2005 .

[36]  S. M. Wilson,et al.  The effects of conformation and solvation on optical rotation: substituted epoxides. , 2008, Chirality.

[37]  T. Daniel Crawford,et al.  Ab initio calculation of molecular chiroptical properties , 2006 .

[38]  J. Tomasi,et al.  Quantum mechanical continuum solvation models. , 2005, Chemical reviews.

[39]  Vincenzo Barone,et al.  A benchmark study of electronic excitation energies, transition moments, and excited-state energy gradients on the nicotine molecule. , 2014, The Journal of chemical physics.

[40]  Jacopo Tomasi,et al.  Modeling solvent effects on chiroptical properties. , 2011, Chirality.

[41]  Kevin McAdam,et al.  Spectroscopic investigations into the acid–base properties of nicotine at different temperatures , 2013 .

[42]  Benedetta Mennucci,et al.  Polarizable continuum model , 2012 .

[43]  M. Parrinello,et al.  Canonical sampling through velocity rescaling. , 2007, The Journal of chemical physics.

[44]  J. Simons,et al.  Structure, electronic circular dichroism and Raman optical activity in the gas phase and in solution: a computational and experimental investigation. , 2005, Physical chemistry chemical physics : PCCP.

[45]  F. Lipparini,et al.  Towards an accurate description of anharmonic infrared spectra in solution within the polarizable continuum model: reaction field, cavity field and nonequilibrium effects. , 2011, The Journal of chemical physics.

[46]  J. Lisowski,et al.  Lanthanide complexes of the chiral hexaaza macrocycle and its meso-type isomer: solvent-controlled helicity inversion. , 2007, Inorganic chemistry.

[47]  R. Fukumoto,et al.  Molecular structure of nicotine as studied by gas electron diffraction combined with theoretical calculations , 2002 .

[48]  B. Testa,et al.  Circular dichroic determination of the preferred conformation of nicotine and related chiral alkaloids in aqueous solution. , 1973, Molecular pharmacology.

[49]  U. Urleb,et al.  Stereoselectivity in β‐cyclodextrin complexation of 1,4‐dihydropyridine derivatives , 1993 .

[50]  C. Cramer,et al.  Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions. , 2009, The journal of physical chemistry. B.

[51]  F. Melendez,et al.  Conformational population distribution of acetylcholine, nicotine and muscarine in vacuum and solution , 2005 .

[52]  K Schulten,et al.  VMD: visual molecular dynamics. , 1996, Journal of molecular graphics.

[53]  V. Barone,et al.  Development and Validation of the B3LYP/N07D Computational Model for Structural Parameter and Magnetic Tensors of Large Free Radicals. , 2008, Journal of chemical theory and computation.

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

[55]  J. Tomasi,et al.  Tuning of NMR and EPR parameters by vibrational averaging and environmental effects: an integrated computational approach , 2013 .

[56]  J. Cheeseman,et al.  Calculation of Raman optical activity spectra of methyl-β-D-glucose incorporating a full molecular dynamics simulation of hydration effects. , 2011, Journal of the American Chemical Society.

[57]  T. Darden,et al.  Particle mesh Ewald: An N⋅log(N) method for Ewald sums in large systems , 1993 .

[58]  P. Wipf,et al.  Solvent effect on optical rotation: A case study of methyloxirane in water. , 2006, Chemphyschem : a European journal of chemical physics and physical chemistry.

[59]  Johann Gasteiger,et al.  Electronegativity equalization: application and parametrization , 1985 .

[60]  Vincenzo Barone,et al.  Linear Response Theory and Electronic Transition Energies for a Fully Polarizable QM/Classical Hamiltonian. , 2012, Journal of chemical theory and computation.

[61]  D. Dougherty,et al.  A computational study of nicotine conformations in the gas phase and in water. , 2000, The Journal of organic chemistry.

[62]  Thomas Bondo Pedersen,et al.  Ab initio calculation and display of the rotary strength tensor in the random phase approximation. Method and model studies , 1995 .