Chemistry at the Frontier with Physics and Computer Science: Theory and Computation

296 Pages·2022·9.451 MB·English

by  Sergio Rampino

Chemistry at the Frontier with Physics
and Computer Science
Theory and Computation
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Chemistry at the
Frontier with Physics
and Computer Science
Theory and Computation
Sergio Rampino
ScuolaNormaleSuperiore
FacultyofScience
Pisa,Italy
Elsevier
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Contents
Biography xi
Preface xiii
1. Introductionandscope
1.1 Introductionandscope 1
1.2 Notationandconventions 4
Part I
Physics and chemistry
2. Thephysicsofmolecularsystems
2.1 Classicalandquantummechanics 9
2.2 TheSchrödingerequationandthemolecularHamiltonian 14
2.3 TheBorn–Oppenheimerapproximation 16
3. Chemicalconceptsandtheirphysicalcounterpart
3.1 Reductionism,emergentism,orfusionism? 19
3.2 Chemicalreactions 21
3.3 Chemicalbonding 23
4. Abriefhistoricalaccount
Part II
Nuclear dynamics and chemical reactions
5. Reactivecollisions
5.1 Atom–diatomcollisions 36
5.2 Theexperimentalperspective:crossedmolecularbeams 40
5.3 Thechemistryoftheinterstellarmedium 42
vii
viii Contents
6. Thepotential-energysurface
6.1 Analyticalformulationsofthepotential-energysurface 45
6.2 Configuration-spacesampling 48
6.3 Visualizationandanalysis:theH+H2reaction 54
7. Theoreticaltreatments
7.1 Classicaltrajectories 59
7.2 Thequantumapproach 64
7.3 Wavepacketmethods 68
8. Fromtheorytocomputing:collinearreactivescattering
withrealwavepackets
8.1 Thereal-wavepacketmethod 75
8.2 Computationalaspects 78
8.3 Thevibrationaleigenvalueproblem 81
9. Fromreactiondynamicstochemicalkinetics
9.1 Thereactionrateconstant 87
9.2 Kinetictreatmentofastrochemicalreactions 88
9.3 Master-equationapproaches 92
10. Application:C+CH+ →C+ +H:anastrochemical
2
reaction
10.1 TheC+CH+→C++Hreaction 95
2
10.2 Thepotential-energysurface 97
10.3 Dynamicsandkinetics 102
11. Towardscomplexity
11.1 Approximatequantummethods 107
11.2 Moleculardynamicsandstochasticapproaches 109
11.3 BeyondtheBorn–Oppenheimerapproximation 112
Part III
Electronic structure and chemical bonding
12. Thewavefunctionandtheelectrondensity
12.1 TheHartree–Fockmodel 121
12.2 Theelectroniccorrelation 128
12.3 Density-functionaltheory 130
Contents ix
13. Fromtheorytocomputing:theHartree–Fockmodel
13.1 TheRoothaan–Hallequations 135
13.2 Self-consistentfieldprocedure 138
13.3 Basisfunctionsandone-andtwo-electronintegrals 140
14. Theatomandthebond
14.1 Partitioningschemes 152
14.2 Thequantumtheoryofatomsinmolecules 156
14.3 Charge-redistributionanalysis 160
15. Fromtheorytocomputing:analyzingthe
electron-chargeredistribution
15.1 Object-basedprogramming 167
15.2 Workingwithdiscretizedelectrondensities 169
15.3 Implementationnotes 172
16. Application:donationandbackdonationin
coordinationchemistry
16.1 Themetal–carbonylcoordinationbond 175
16.2 Bondpropertiesandexperimentalobservables 178
16.3 Selectivelyprobingσ-donationandπ-backdonation 182
17. Relativityandchemistry
17.1 Relativisticquantumchemistry 191
17.2 Dirac–Kohn–Shamcalculations 195
17.3 Relativityandtheperiodictable 199
Part IV
Chemistry and computer science
18. Scientificcomputing
18.1 Scientificprogramming 207
18.2 High-performanceandhigh-throughputcomputing 210
18.3 ParallelizingaDirac–Kohn–Shamprogram 215
19. Virtualreality
19.1 Scientificvisualizationandvirtualreality 221
19.2 Awalkthroughchemistry:immersiveexplorationof
potential-energylandscapes 224
19.3 Chemistryatyourfingertips:animmersivelaboratoryforthe
analysisofchemicalbonding 229