Top Organomet Chem (2020) 67: 1–38
https://doi.org/10.1007/3418_2020_57
# Springer Nature Switzerland AG 2020
Published online: 28 July 2020
What Makes a Good (Computed) Energy
Profile?
Odile Eisenstein, Gregori Ujaque, and Agustí Lledós
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2 Reality and Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3 The Challenges . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. 7
4 The Chemical Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.1 What’s Inside the Flask? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.2 Conformational Complexity . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . .. . . 15
5 The Theoretical Model . . . . . . . . . . . . .. . . . . . . . . . . . . . .. . . . . . . . . . . . . .. . . . . . . . . . . . . .. . . . . . . . . . . . . .. . 18
5.1 Electronic Structure Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
5.2 Spin-State Energetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
5.3 Entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
6 The Solvent: Chemical and Theoretical Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
7 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
Abstract A good meal cannot be defined in an absolute manner since it depends
strongly on where and how it is eaten and how many people participate. A picnic
shared by hikers after a challenging climbing is very different from a birthday party
among a family or a banquet for a large convention. All of them can be memorable
and also good. The same perspective applies to computational studies. Required
level of calculations for spectroscopic properties of small molecular systems and
properties of medium or large organic or organometallic, polymetallic systems are
different. To well-specified chemical questions and chemical systems, efficient
O. Eisenstein
Department of Chemistry and Hylleraas Centre for Quantum Molecular Sciences, University of
Oslo, Oslo, Norway
ICGM, Université de Montpellier, CNRS, ENSCM, Montpellier, France
G. Ujaque and A. Lledós (*)
Departament de Química and Centro de Innovación en Química Avanzada (ORFEO-CINQA),
Universitat Autònoma de Barcelona, Catalonia, Spain
e-mail: agusti@klingon.uab.es
https://doi.org/10.1007/3418_2020_57
# Springer Nature Switzerland AG 2020
Published online: 28 July 2020
What Makes a Good (Computed) Energy
Profile?
Odile Eisenstein, Gregori Ujaque, and Agustí Lledós
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2 Reality and Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3 The Challenges . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. 7
4 The Chemical Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.1 What’s Inside the Flask? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.2 Conformational Complexity . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . .. . . 15
5 The Theoretical Model . . . . . . . . . . . . .. . . . . . . . . . . . . . .. . . . . . . . . . . . . .. . . . . . . . . . . . . .. . . . . . . . . . . . . .. . 18
5.1 Electronic Structure Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
5.2 Spin-State Energetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
5.3 Entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
6 The Solvent: Chemical and Theoretical Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
7 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
Abstract A good meal cannot be defined in an absolute manner since it depends
strongly on where and how it is eaten and how many people participate. A picnic
shared by hikers after a challenging climbing is very different from a birthday party
among a family or a banquet for a large convention. All of them can be memorable
and also good. The same perspective applies to computational studies. Required
level of calculations for spectroscopic properties of small molecular systems and
properties of medium or large organic or organometallic, polymetallic systems are
different. To well-specified chemical questions and chemical systems, efficient
O. Eisenstein
Department of Chemistry and Hylleraas Centre for Quantum Molecular Sciences, University of
Oslo, Oslo, Norway
ICGM, Université de Montpellier, CNRS, ENSCM, Montpellier, France
G. Ujaque and A. Lledós (*)
Departament de Química and Centro de Innovación en Química Avanzada (ORFEO-CINQA),
Universitat Autònoma de Barcelona, Catalonia, Spain
e-mail: agusti@klingon.uab.es