THEORETICAL METHODS IN CONDENSED PHASE CHEMISTRY

By STEVEN MARTINEZ

CONTENTS I INTRODUCTION III VARIATIONAL RATE THEORY IV TURNOVER THEORY V QUANTUM RATE THEORY VI DISCUSSION CLASSICAL AND QUANTUM RATE THEORY FOR CONDENSED PHASES THE GLE AS A PARADIGM OF CONDENSED PHASE SYSTEMS FEYNMANPATH CENTROID DYNAMICS II THE CENTROID DISTRIBUTION FUNCTION III EXACT FORMULATION OFCENTROID DYNAMICS IV THE CENTROID MOLECULAR DYNAMICS APPROXIMATION V SOME APPLICATIONS OF CENTROID MOLECULARDYNAMICS VI CONCLUDING REMARKS PROTON TRANSFER IN CONDENSED PHASES: BEYOND THE QUANTUM KRAMERS PARADIGM I INTRODUCTION II CALCULATION OF QUANTUM TRANSFER RATES IV POSITION-DEPENDENT FRICTION III RATEPROMOTING VIBRATIONS V EFFECT OFLOW-FREQUENCY MODES OF THE ENVIRONMENT VI CONCLUSIONS NONSTATIONARY STOCHASTIC DYNAMICS AND APPLICATIONS TO CHEMICALPHYSICS I INTRODUCTION III APPLICATION TO POLYMER SYSTEMS II NONSTATIONARY STOCHASTIC MODELS IV APPLICATION TO PROTEIN FOLDING V CONCLUDING REMARKS II THE THOMAS-FERMI MODEL AND EXTENSIONS III THE VON WEIZSÄCKER MODEL AND EXTENSIONS IV CORRECT RESPONSE BEHAVIOR V NONLOCAL DENSITY APPROXIMATIONS VI NUMERICAL IMPLEMENTATIONS VII APPLICATIONS AND FUTURE PROSPECTS ORBITAL-FREE KINETIC-ENERGY DENSITY FUNCTIONAL THEORY SEMICLASSICAL SURFACE HOPPING METHODS FOR NONADIABATIC TRANSITIONS IN CONDENSEDPHASES I INTRODUCTION 11 SEMICLASSICAL SURFACE-HOPPING METHODS FOR NONADIABATICPROBLEMS IV SUMMARY II THE BASICS OF SOLVATION DYNAMICS III SOLVATION DYNAMICS WITHIN THE LINEAR RESPONSE APPROXIMATION IV NONLINEAR SOLVATION RESPONSE V SUMMARY III NUMERICAL CALCULATIONS OF VIBRATIONAL POPULATION RELAXATION MECHANISTIC STUDIES OF SOLVATION DYNAMICS IN LIQUIDS THEORETICAL CHEMISTRY OF HETEROGENEOUS REACTIONS OF ATMOSPHERIC IMPORTANCE: THE HCL+CLONO2 REACTION ON ICE I INTRODUCTION II HCL+ CLONO2 ? CL 2 + HNO3 ON ICE III IV CONCLUDING REMARKS – + CLONO2 ?CL2 + NO_ 3 ON ICE SIMULATION OF CHAMICAL REACTIONS IN SOLUTION USING AN AB INITIO MOLECULAR ORBITAL-VALENCE BOND MODEL I INTRODUCTION II METHODS III FREE ENERGYSIMULATIONMETHOD IV COMPUTATIONAL DETAILS V RESULTS AND DISCUSSION METHODS FOR FINDING SADDLE POINTS AND MINIMUM ENERGY PATHS I INTRODUCTION II THE DRAG METHOD III THENEB METHOD IV THE CI-NEB METHOD V THE CPR METHOD VI THE RIDGE METHOD VII THE DHS METHOD 28 VIII THE DIMER METHOD X RESULTS XI DISCUSSION XII SUMMARY APPENDIX: THE TWO-DIMENSIONAL TEST PROBLEM