Koopmans' theorem states that in closedshell Hartree–Fock theory, the first ionization energy of a molecular system is equal to the negative of the orbital energy of the highest occupied molecular orbital (HOMO). This theorem is named after Tjalling Koopmans, who published this result in 1934.^{[1]} Koopmans became a Nobel laureate in 1975, though neither in physics nor chemistry, but in economics.
Koopmans' theorem is exact in the context of restricted Hartree–Fock theory if it is assumed that the orbitals of the ion are identical to those of the neutral molecule (the frozen orbital approximation). Ionization energies calculated this way are in qualitative agreement with experiment – the first ionization energy of small molecules is often calculated with an error of less than two electron volts.^{[2]}^{[3]}^{[4]} Therefore, the validity of Koopmans' theorem is intimately tied to the accuracy of the underlying Hartree–Fock wavefunction. The two main sources of error are:

orbital relaxation, which refers to the changes in the Fock operator and Hartree–Fock orbitals when changing the number of electrons in the system, and

electron correlation, referring to the validity of representing the entire manybody wavefunction using the Hartree–Fock wavefunction, i.e. a single Slater determinant composed of orbitals that are the eigenfunctions of the corresponding selfconsistent Fock operator.
Empirical comparisons with experimental values and higherquality ab initio calculations suggest that in many cases, but not all, the energetic corrections due to relaxation effects nearly cancel the corrections due to electron correlation.^{[5]}^{[6]}
A similar theorem exists in density functional theory (DFT) for relating the exact first vertical ionization energy and electron affinity to the HOMO and LUMO energies, although both the derivation and the precise statement differ from that of Koopmans' theorem. Ionization energies calculated from DFT orbital energies are usually poorer than those of Koopmans' theorem, with errors much larger than two electron volts possible depending on the exchangecorrelation approximation employed.^{[2]}^{[3]} The LUMO energy shows little correlation with the electron affinity with typical approximations.^{[7]} The error in the DFT counterpart of Koopmans' theorem is a result of the approximation employed for the exchange correlation energy functional so that, unlike in HF theory, there is the possibility of improved results with the development of better approximations.
Contents

Generalizations of Koopmans' theorem 1

Groundstate and excitedstate ions 1.1

Koopmans' theorem for electron affinities 1.2

Koopmans' theorem for openshell systems 1.3

Counterpart in density functional theory 2

References 3

External links 4
Generalizations of Koopmans' theorem
While Koopmans' theorem was originally stated for calculating ionization energies from restricted (closedshell) Hartree–Fock wavefunctions, the term has since taken on a more generalized meaning as a way of using orbital energies to calculate energy changes due to changes in the number of electrons in a system.
Groundstate and excitedstate ions
Koopmans’ theorem applies to the removal of an electron from any occupied molecular orbital to form a positive ion. Removal of the electron from different occupied molecular orbitals leads to the ion in different electronic states. The lowest of these states is the ground state and this often, but not always, arises from removal of the electron from the HOMO. The other states are excited electronic states.
For example the electronic configuration of the H_{2}O molecule is (1a_{1})^{2} (2a_{1})^{2} (1b_{2})^{2} (3a_{1})^{2} (1b_{1})^{2},^{[8]} where the symbols a_{1}, b_{2} and b_{1} are orbital labels based on molecular symmetry. From Koopmans’ theorem the energy of the 1b_{1} HOMO corresponds to the ionization energy to form the H_{2}O^{+} ion in its ground state (1a_{1})^{2} (2a_{1})^{2} (1b_{2})^{2} (3a_{1})^{2} (1b_{1})^{1}. The energy of the secondhighest MO 3a_{1} refers to the ion in the excited state (1a_{1})^{2} (2a_{1})^{2} (1b_{2})^{2} (3a_{1})^{1} (1b_{1})^{2}, and so on. In this case the order of the ion electronic states corresponds to the order of the orbital energies. Excitedstate ionization energies can be measured by photoelectron spectroscopy.
For H_{2}O, the nearHartree–Fock orbital energies (with sign changed) of these orbitals are 1a_{1} 559.5, 2a_{1} 36.7 1b_{2} 19.5, 3a_{1} 15.9 and 1b_{1} 13.8 eV. The corresponding ionization energies are 539.7, 32.2, 18.5, 14.7 and 12.6 eV.^{[8]} As explained above, the deviations are due to the effects of orbital relaxation as well as differences in electron correlation energy between the molecular and the various ionized states.
For N_{2} in contrast, the order of orbital energies is not identical to the order of ionization energies. NearHartree–Fock calculations with a large basis set indicate that the 1π_{u} bonding orbital is the HOMO. However the lowest ionization energy corresponds to removal of an electron from the 3σ_{g} bonding orbital. In this case the deviation is attributed primarily to the difference in correlation energy between the two orbitals.^{[9]}
Koopmans' theorem for electron affinities
It is sometimes claimed^{[10]} that Koopmans' theorem also allows the calculation of electron affinities as the energy of the lowest unoccupied molecular orbitals (LUMO) of the respective systems. However, Koopmans' original paper makes no claim with regard to the significance of eigenvalues of the Fock operator other than that corresponding to the HOMO. Nevertheless, it is straightforward to generalize the original statement of Koopmans' to calculate the electron affinity in this sense.
Calculations of electron affinities using this statement of Koopmans' theorem have been criticized^{[11]} on the grounds that virtual (unoccupied) orbitals do not have wellfounded physical interpretations, and that their orbital energies are very sensitive to the choice of basis set used in the calculation. As the basis set becomes more complete; more and more "molecular" orbitals that are not really on the molecule of interest will appear, and care must be taken not to use these orbitals for estimating electron affinities.
Comparisons with experiment and higherquality calculations show that electron affinities predicted in this manner are generally quite poor.
Koopmans' theorem for openshell systems
Koopmans' theorem is also applicable to openshell systems. It was previously believed that this was only in the case for removing the unpaired electron,^{[12]} but the validity of Koopmans’ theorem for ROHF in general has been proven provided that the correct orbital energies are used.^{[13]}^{[14]}^{[15]}^{[16]} The spin up (alpha) and spin down (beta) orbital energies do not necessarily have to be the same.^{[17]}
Counterpart in density functional theory
Kohn–Sham (KS) density functional theory (KSDFT) admits its own version of Koopmans' theorem (sometimes called the DFTKoopmans' theorem) very similar in spirit to that of Hartree Fock theory. The theorem equates the first (vertical) ionization energy I of a system of N electrons to the negative of the corresponding KS HOMO energy \epsilon_H . More generally, this relation is true even when the KS systems describes a zerotemperature ensemble with noninteger number of electrons N  \delta N for integer N and \delta N \rightarrow 0. When considering N + \delta N electrons the infinitesimal excess charge enters the KS LUMO of the N electron system but then the exact KS potential jumps by a constant known as the "derivative discontinuity".^{[18]} It can be shown that the vertical electron affinity is equal exactly to the negative of the sum of the LUMO energy and the derivative discontinuity.^{[18]}^{[19]}
Unlike the approximate status of Koopmans' theorem in Hartree Fock theory (because of the neglect of orbital relaxation), in the exact KS mapping the theorem is exact, including the effect of orbital relaxation. A sketchy proof of this exact relation goes in three stages. First, for any finite system I determines the \bold{r}\rightarrow\infty asymptotic form of the density, which decays as n(\bold{r})\rightarrow e^{2\sqrt{\frac{2 m_e}{\hbar} I}\bold{r}}.^{[18]} ^{[20]} Next, as a corollary (since the physically interacting system has the same density as the KS system), both must have the same ionization energy. Finally, since the KS potential is zero at infinity, the ionization energy of the KS system is, by definition, the negative of its HOMO energy and thus finally: \epsilon_H = I , QED.
While these are exact statements in the formalism of DFT, the use of approximate exchangecorrelation potentials makes the calculated energies approximate and often the orbital energies are very different from the corresponding ionization energies (even by several eVs!).^{[21]}
A tuning procedure is able to "impose" Koopmans' theorem on DFT approximations thereby improving many of its related predictions in actual applications. ^{[21]}^{[22]}
In approximate DFTs one can estimate to high degree of accuracy the deviance from Koopmans' theorem using the concept of energy curvature.^{[23]}
References

^ Koopmans, Tjalling (1934). "Über die Zuordnung von Wellenfunktionen und Eigenwerten zu den einzelnen Elektronen eines Atoms". Physica (Elsevier) 1 (1–6): 104–113.

^ ^{a} ^{b} Politzer, Peter; AbuAwwad, Fakher (1998). "A comparative analysis of Hartree–Fock and Kohn–Sham orbital energies". Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta) 99 (2): 83–87.

^ ^{a} ^{b} Hamel, Sebastien; Duffyc, Patrick; Casidad, Mark E.; Salahub, Dennis R. (2002). "Kohn–Sham orbitals and orbital energies: fictitious constructs but good approximations all the same". Journal of Electron Spectroscopy and Related Phenomena 123 (2–3): 345–363.

^ See, for example, Szabo, A.; Ostlund, N. S. "Chapter 3". Modern Quantum Chemistry.

^ Michl, Josef; BonačićKoutecký, Vlasta (1990). Electronic Aspects of Organic Photochemistry. Wiley. p. 35.

^ Hehre, Warren J.; Radom, Leo; Schleyer, Paul v.R.; Pople, John A. (1986). Ab initio molecular orbital theory. Wiley. p. 24.

^ Zhang, Gang; Musgrave, Charles B. (2007). "Comparison of DFT Methods for Molecular Orbital Eigenvalue Calculations". The Journal of Physical Chemistry A 111 (8): 1554–1561.

^ ^{a} ^{b} Levine, I. N. (1991). Quantum Chemistry (4th ed.). PrenticeHall. p. 475.

^ Duke, Brian J.; O'Leary, Brian (1995). "NonKoopmans' Molecules". Journal of Chemical Education 72 (6): 501.

^ See, for example, Szabo, A.; Ostlund, N. S. Modern Quantum Chemistry. p. 127.

^ Jensen, Frank (1990). Introduction to Computational Chemistry. Wiley. pp. 64–65.

^ Fulde, Peter (1995). Electron correlations in molecules and solids. Springer. pp. 25–26.

^ Plakhutin, B. N.; Gorelik, E. V.; Breslavskaya, N. N. (2006). "Koopmans' theorem in the ROHF method: Canonical form for the HartreeFock Hamiltonian". The Journal of Chemical Physics 125 (20): 204110.

^ Davidson, Ernest R.; Plakhutin, Boris N. (2010). "Koopmans's theorem in the restricted openshell Hartree–Fock method. II. The second canonical set for orbitals and orbital energies". The Journal of Chemical Physics 132 (18): 184110.

^ Plakhutin, Boris N.; Davidson, Ernest R. (2009). "Koopmans' Theorem in the Restricted OpenShell Hartree−Fock Method. 1. A Variational Approach†". The Journal of Physical Chemistry A 113 (45): 12386–12395.

^ Glaesemann, Kurt R.; Schmidt, Michael W. (2010). "On the Ordering of Orbital Energies in HighSpin ROHF†". The Journal of Physical Chemistry A 114 (33): 8772–8777.

^ Tsuchimochi, Takashi; Scuseria, Gustavo E. (2010). "Communication: ROHF theory made simple". The Journal of Chemical Physics 133 (14): 141102.

^ ^{a} ^{b} ^{c} Perdew, John P.; Parr, Robert G.; Levy, Mel; Balduz, Jr., Jose L. (1982). "DensityFunctional Theory for Fractional Particle Number: Derivative Discontinuities of the Energy". Physical Review Letters 49 (23): 1691–1694.

^ Perdew, John P.; Levy, Mel (1997). "Comment on "Significance of the highest occupied Kohn–Sham eigenvalue"". Physical Review B 56 (24): 16021–16028.

^ Almbladh, C. O.; von Barth, U. (1985). "Exact results for the charge and spin densities, exchangecorrelation potentials, and densityfunctional eigenvalues". Physical Review B 31 (6): 3231.

^ ^{a} ^{b} Salzner, U.; Baer, R. (2009). "Koopmans' springs to life". The Journal of Chemical Physics 131 (23): 231101–4.

^ Baer, R.; Livshits, E.; Salzner, U. (2010). ""Tuned" Rangeseparated hybrids in density functional theory". Annual Review of Physical Chemistry 61: 85–109.

^ Stein, Tamar; Autschbach, Jochen; Govind, Niranjan; Kronik, Leeor; Baer, Roi (2012). "Curvature and frontier orbital energies in density functional theory". The Journal of Physical Chemistry Letters 3 (24): 3740.
External links

Bowman, Joel. "Lecture on Koopmans' Theorem Chem 531".

"Koopmans' autobiography". The Nobel Foundation. 1975.
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