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6

ISSN 1430-4171

THE CHEMICAL EDUCATOR

http://journals.springer-ny.com/chedr

© 1997 SPRINGER-VERLAG NEW YORK, INC.

10.1007/s00897970153a

In the Classroom

Kinetic Energy

and the Covalent

+

Bond in H2

FRANK RIOUX

Department of Chemistry

St. John’s University

College of St. Benedict

St. Joseph, MN 56374

frioux@csbsju.edu

Using a

reasonably

accurate wave

function, he

A

**modified version of Ruedenberg’s innovative
**

analysis of the chemical bond in the hydrogen

molecule ion is presented that factors the bond

energy

into

bonding

and

nonbonding

contributions. This simplified approach clearly illustrates

Ruedenberg’s main thesis: chemical bond formation is driven

by a decrease in electron kinetic energy.

described the

formation of the

chemical bond in

terms of both

kinetic and

potential energy.

Introduction

**In 1962, Ruedenberg [1] published a persuasive quantum
**

mechanical analysis of the hydrogen molecule ion that

challenged the prevailing opinion that covalent bonding is

simply an electrostatic phenomenon, by demonstrating the

crucial importance of kinetic energy in chemical bond

formation. In the ensuing years, Ruedenberg, in collaboration

with others, extended and refined his original study [2–4].

While this important work has received some attention in the

pedagogical literature [5–7], and brief treatment in a few

and the bonding term is identical to his interference term. this paper employs a more elementary analysis that partitions the bond energy into just two contributions: bonding and nonbonding. EH 2 + = 〈 Ψ H Ψ〉 = 〈 a + b H a + b〉 H aa + H ab = 2 + 2S 1+ S (3) . S 1430-4171 (97)06153-2 advanced texts [7–11]. INC. 6 ISSN 1430-4171 THE CHEMICAL EDUCATOR http://journals. Ruedenberg revealed the critical role of kinetic energy in bond formation by partitioning the bond energy into three contributions that he called quasi-classical. is a variational parameter that controls the spatial extent of the wave function. The variation integral is. we have Ψ= a+b 2 + 2S (1) where.com/chedr © 1997 SPRINGER-VERLAG NEW YORK. NO. chemistry textbooks currently in use throughout the undergraduate curriculum present exclusively the conventional view that the covalent bond can be understood solely in terms of electrostatic potential energy. as was first suggested by Finkelstein and Horowitz [12]. 2.2 / VOL.springer-ny. This simplification comes at some cost in understanding the finer details of chemical bond formation. + Calculating the Ground State of H2 + Writing the molecular orbital in H2 as a linear combination of scaled hydrogenic 1s orbitals centered on nuclei a and b. but the main message comes across clearly: kinetic energy plays an essential role in the formation of a stable covalent bond. promotion. α3 a= exp(− αra ) π α3 b= exp(− αrb ) π S= a b (2) The scale factor or decay constant. α. In an effort to make this important conclusion accessible to undergraduates. The nonbonding term is the sum of Ruedenberg’s quasi-classical and promotion contributions. and interference [4].

and the last term the operator for nuclear–nuclear repulsion.springer-ny. 6 ISSN 1430-4171 THE CHEMICAL EDUCATOR http://journals. In other words. INC. When the matrix elements are evaluated. the electron density in a plane containing the bond axis is shown in Figure 2. it is possible to resolve the total . Fortunately. it is possible to construct a nonbonding state 2 within the LCAO-MO approach and subtract it from |Ψ| to get a physical picture of the nature of the chemical bond. The energy operator is given by. S 1430-4171 (97)06153-2 where due to the symmetry of the molecule Haa = Hbb and Hab = Hba.com/chedr © 1997 SPRINGER-VERLAG NEW YORK. The energy operator above and the calculation outlined below are expressed in atomic units (|e| = me = h/(2π) = 4πε0 = 1).0033 bohr.5865 hartree. α. the second and third terms represent the electrostatic interaction between the electron and the two nuclei. a 2 + b2 + 2ab Ψ = 2 + 2S 2 (6) Identifying the Nonbonding Electron Density An important question at this point is how much of the electron density represented by 2 |Ψ| contributes to bonding. with both surface and contour representations.2387 and E H + = –0. NO. is obtained [13].3 / VOL. with α = 1. the first term is the electron kinetic energy operator. 2. Minimization of the energy simultaneously + with respect to α and R locates the H2 ground state at Re = 2. 2 For the ground state calculated above. the following expression in the scale factor. and the internuclear separation. 1 1 1 1 H = − ∇2 − − + 2 ra rb R (4) In eq 4. EH 2 + =− α + 2 2 α2 −α − 1 1 + + α exp(− 2αR) + α (α − 2)(1 + αR) exp(− αR) 1 R R + R α 2 R2 1 + exp(− αR)1 + αR + 3 (5) Minimization of the energy with respect to α as a function of R yields the molecular potential-energy curve shown in Figure 1. R.

Ψn = a + ib 2 (7) The energy associated with the nonbonding electron density is En = 〈 Ψn H Ψn 〉 = 〈 a − ib H a + ib〉 H aa + H bb = = H aa 2 2 (8) The explicit form of En in terms of α and R can be shown to be [13] 1 α2 1 1 − α − − α + exp(− 2αR) + En = 2 R R R (9) .springer-ny. 2. INC. NO. S 1430-4171 (97)06153-2 FIGURE 1. electron density into atomic and molecular contributions. The nonbonding electron density is described by a wavefunction in which the hydrogen atomic orbitals are 90° out of phase [14]. MOLECULAR POTENTIAL-ENERGY CURVE FOR H2+.4 / VOL. 6 ISSN 1430-4171 THE CHEMICAL EDUCATOR http://journals.com/chedr © 1997 SPRINGER-VERLAG NEW YORK.

|Ψ|2. Later we will be able to show exactly how much charge density difference there is between these two wave functions in the internuclear region. where the first term on the right is the kinetic energy of the electron in orbital a. Figure 3 shows surface and contour plots of the nonbonding electron density.com/chedr © 1997 SPRINGER-VERLAG NEW YORK. the second term is the electron’s electrostatic interaction with nucleus a. 6 ISSN 1430-4171 THE CHEMICAL EDUCATOR http://journals.5 / VOL. The distribution of contours also confirms that the nonbonding state has more atomic character. INC. and the fourth term is the nuclear–nuclear repulsion. .springer-ny. 2. Ψn = 2 a 2 + b2 2 (10) A qualitative comparison of Figures 2 and 3 shows that there is less electron density in the internuclear region in the nonbonding state. TOTAL ELECTRON DENSITY. the third term is its interaction with nucleus b. NO. S 1430-4171 (97)06153-2 FIGURE 2.

Isolating the Bonding Electron Density It is now possible to partition E H + into bonding and nonbonding contributions using 2 En = Haa.springer-ny.5 hartree and E H + = 0. |Ψn| . while noting that EH = –0. 6 ISSN 1430-4171 THE CHEMICAL EDUCATOR http://journals. S 1430-4171 (97)06153-2 2 FIGURE 3.6 / VOL. NONBONDING ELECTRON DENSITY. which has its origin in the constructive overlap of the atomic orbitals. This expression can be used to examine the behavior of the bond energy as a function of the internuclear separation. INC. R. ∆Ebond = E H 2 + − EH − EH + Combining eqs 11 and 12. yields (12) . EH 2 + = En + H ab H − SH aa = En + ab = En + Eb 1+ S 1+ S (11) where Eb is the energy due to the bonding electron density. 2. NO.com/chedr © 1997 SPRINGER-VERLAG NEW YORK.

This increase in potential energy is funded by a larger decrease in kinetic energy due to the delocalization of electron density. It also shows that this charge buildup came from the regions immediately around the nuclei. En is the energy 2 2 2 2 associated with the nonbonding electron density. is shown in Figure 6 as both surface and contour plots. S 1430-4171 (97)06153-2 1 1 ∆Ebond = E H + + = En + + Eb 2 2 2 (13) These terms are plotted as a function of R in Figure 4. Eb = E H 2 + − En (14) 2 E H + is the energy associated with the total electron density. . NO.springer-ny. Ψb = Ψ − Ψn 2 2 2 2 2ab − Sa 2 − Sb 2 = 2 + 2S (15) The bonding electron density.com/chedr © 1997 SPRINGER-VERLAG NEW YORK. |Ψn| . This explains why Vb is positive in Figure 5. based on the partitioning given in eq 13. the formation of a stable chemical bond by transfer of charge into the internuclear region. |Ψb| .7 / VOL. In other words. and that the state represented by Ψn is indeed nonbonding for all values of R. transferring electron density from the nuclei to the internuclear region increases potential energy. |Ψ| . 2. Table 1 provides a breakdown of the + contributions to the H2 bond energy. Therefore. when Eb is separated into its kinetic and potential energy components. This figure clearly shows the buildup of charge in the internuclear region. electron sharing. this is frequently referred to as the glue that holds the nuclei together in a chemical bond. Furthermore. is driven by a decrease in kinetic energy. + A graphical representation of the covalent bond in H2 can be found by isolating the bonding energy term and extracting from it the bonding electron density. Figure 5 shows that the Tb term is responsible for the energy minimum in the hydrogen molecule ion. 6 ISSN 1430-4171 THE CHEMICAL EDUCATOR http://journals. More will be said about these entries in a moment. |Ψ| – |Ψn| is the bonding electron density with energy Eb. This figure clearly shows that Eb is the cause of stable bond formation. INC.

17301 ∆E/hartree –0.8 / VOL.08651 . INC. 2. PARTITIONING OF BOND ENERGY INTO BONDING AND NONBONDING CONTRIBUTIONS.springer-ny.26636 0.com/chedr © 1997 SPRINGER-VERLAG NEW YORK. S 1430-4171 (97)06153-2 FIGURE 4.22585 –0.05284 –0. Bond Energy Contributions for H2 (a) Bonding (b) Nonbonding Total ∆T/hartree –0. 6 ISSN 1430-4171 THE CHEMICAL EDUCATOR http://journals.04051 –0. NO.12702 0.17985 0. + Table 1.08651 ∆V/hartree 0.

Mechanism for Covalent Bond Formation Figure 7 juxtaposes plots of the total electron density. 2.com/chedr S 1430-4171 (97)06153-2 FIGURE 5. and nonbonding density along the bond axis. Experiment yields a target bond energy while a quantum mechanical model (Born– Oppenheimer approximation. On the basis of the model presented in this study. cannot be subjected to direct empirical test. ISSN 1430-4171 http://journals. the formation of a covalent bond is interpreted in terms of two phenomena: charge delocalization and orbital contraction. Finkelstein–Horowitz wave function. however. Both it and Table 1 can now be used to provide a synopsis of covalent bond formation in the hydrogen molecule ion. NO. 6 THE CHEMICAL EDUCATOR © 1997 SPRINGER-VERLAG NEW YORK.9 / VOL. LCAO-MO. we gain confidence in the model. If the comparison is favorable.springer-ny. INC. PARTITIONING OF BONDING ENERGY INTO KINETIC (Tb) AND POTENTIAL (Vb) ENERGY CONTRIBUTIONS. etc. constructive interference due to the overlap .) enables us to calculate a theoretical bond energy. (a) Under the LCAO-MO approximation. bonding density. and may use it to create a mechanism for bond formation whose individual steps.

10 / VOL. or ∆E = ∆V/2).01 0. that chemical bonding can be understood solely in electrostatic terms. NO. we see that the sum of processes (a) and (b) is. 6 ISSN 1430-4171 THE CHEMICAL EDUCATOR http://journals. and their ratio satisfies the virial theorem (∆V = –2∆T. by which the virial theorem is satisfied.005 0. but erroneous belief.02 0. 2.005 0.015 0.015 0. Overall.02 0. BONDING ELECTRON DENSITY.005 0 0.01 0. causing a large decrease in potential energy and a slightly larger increase in kinetic energy (see the nonbonding column in Table 1). S 1430-4171 (97)06153-2 0 0 0.01 0 0.025 0. This delocalization of electron density decreases kinetic energy more than it increases potential energy (see the bonding column in Table 1). and endothermic. |Ψb|2.005 0.005 0.005 0 0 FIGURE 6. α). This is the origin of the widely held.015 0. of atomic orbitals transfers charge from the nonbonding areas immediately surrounding the nuclei to the internuclear region.025 0.com/chedr © 1997 SPRINGER-VERLAG NEW YORK. (b) The consequent reduction of electron density at the nuclear centers allows the atomic orbitals to contract (increasing the scale factor. negative.06 0.01 0. Process (b) is atomic or nonbonding. INC. . ∆T is positive and ∆V is negative. of course.03 0.03 0. The large drop in potential energy in step (b). indicating molecular stability for + H2 .015 0. is caused by a contraction of atomic orbitals that actually draws electron density out of the bond region toward the nuclei. and exothermic.springer-ny. as Figure 7 clearly shows.01 0.06 0.005 0. Process (a) is molecular or bonding. Looking at the last row (∆E) of Table 1.

|Ψ(x)|2. TOTAL ELECTRON DENSITY. |Ψn(x)|2.0033.4631.577S 2 ) (16) For α = 1. INC. S.springer-ny.738S (1 − S ) 1 − 0.11 / VOL. ( Bonding Charge = 0. the amount of charge within this region is given by a polynomial in the overlap integral. S 1430-4171 (97)06153-2 FIGURE 7. NO. 6 ISSN 1430-4171 THE CHEMICAL EDUCATOR http://journals. Ruedenberg [4] showed that for the Finkelstein–Horowitz wave function used in this study. This small . 2. Now we deal with the question of how much charge is actually transferred to the internuclear region. AND BONDING ELECTRON DENSITY.2387 and R = 2. or 16%. NONBONDING ELECTRON DENSITY. This is calculated as the electron density between the hyperbolic nodes shown in Figure 6.com/chedr © 1997 SPRINGER-VERLAG NEW YORK. |Ψb(x)|2. the overlap integral is 0.16 electrons. and the charge transferred to the bonding region is calculated to be 0. ALONG THE BOND AXIS.

note.12 / VOL. Conclusion This brings us to the necessity and importance of models. is a mechanism for funding the transfer of charge into the bond region. but also consistent with rigorous quantum mechanical principles. The importance of kinetic energy is also manifested by changes in mass. as eq 17 + suggests. which has a mass 207 times that of the electron. “the more accurate the calculations became the more the concepts tended to vanish into thin air” [15]. Actually Ruedenberg’s finding about the importance of kinetic energy in chemical bonding should not be surprising. Using a reasonably accurate wave function. do not collapse into the nucleus under the attractive electrostatic interaction. and that corresponds to an exact solution of the Schrödinger equation” [14]. INC. NO. not simply a sharing by the nuclei. he described the formation of the chemical bond in terms of both kinetic and potential energy. “At + the fundamental level there is only one theory of binding in H2 . A dramatic example of this occurs when the electron in H2 is replaced by the – negative muon (µ ).springer-ny. non-quantum-mechanical models for chemical bonding. The kinetic . as Ruedenberg has shown.com/chedr © 1997 SPRINGER-VERLAG NEW YORK. The seminal idea in quantum theory is de Broglie’s hypothesis that matter has wavelike properties and a wavelength that is inversely proportional to its momentum. we explore different levels of theory and propose models of varying degrees of sophistication to find explanations that are intelligible in terms of familiar concepts. 2. This equation is easily transformed into the following expression for the kinetic energy. Therefore. These models frequently describe an electron-pair bond as a sharing of electrons between the nuclei. 6 ISSN 1430-4171 THE CHEMICAL EDUCATOR http://journals. S 1430-4171 (97)06153-2 percentage is in striking contrast to the kind of electron sharing that is implied by qualitative. h2 T= 2mλ2 (17) Confinement of charge restricts λ to small values. as Robert Mulliken observed. As Melrose et al. for example. Conversely. However. This is what Ruedenberg accomplished in his compelling analysis of the chemical bond. which increases kinetic energy and explains why electrons. delocalization of charge decreases kinetic energy and.

Phys. it is also possible to prepare a qualitative summary of the most important features of the model. so the phenomenon can be attributed solely to the effect of mass on kinetic energy. 1971. Mod. 55. and 7. However. 1962.. M. we minimize the total energy (kinetic and potential) with respect to variational parameters built into the trial wave function. 1971.. Ruedenberg. and the molecule achieves a new equilibrium configuration with a bond length approximately 200 times + shorter than that for H2 [16]. J. allowing the atomic orbitals to shrink.com/chedr S 1430-4171 (97)06153-2 energy initially decreases. Rev. of course. Chem. 326–352. REFERENCES 1. Such a qualitative approach could be used in general chemistry. ISSN 1430-4171 http://journals. Feinberg. Ruedenberg.springer-ny. M. J. 3. Phys. 54. Therefore. In addition I wish to acknowledge helpful discussions with Professors Klaus Ruedenberg and Mark Gordon of Iowa State University prior to the preparation of this manuscript. for example. K. similar effects are observed at the atomic level with species like positronium and muonium. . 2. And. Feinberg. Jeffry Madura of the University of South Alabama. Ruedenberg. 34. based solely on Figures 2. 6 THE CHEMICAL EDUCATOR © 1997 SPRINGER-VERLAG NEW YORK. The model for covalent bonding outlined here has been presented using only the most elementary principles of ab initio quantum mechanics. K. Phys. J. 2. Thomas. and Dennis Rioux of the University of WisconsinOshkosh. 5804. When we perform ab initio quantum mechanical calculations on atoms and molecules. I also appreciate suggestions made by Joe Brom of the University of St.13 / VOL. nothing is changed by this electron– muon exchange. and is therefore appropriate for a physical chemistry course that includes the study of quantum chemistry. INC. Chem. Brian Johnson. K. we should expect that a correct interpretation of the results of the calculations requires consideration of both kinetic and potential energy contributions. ACKNOWLEDGEMENT I wish to thank my department colleagues Kate Graham. NO. 6. J. or for any advanced course dealing with chemical bonding that has the appropriate physicalchemistry prerequisite. 1495–1511. Electrostatically. Phil Karjala. to present an alternative to the strictly electrostatic model of covalent bonding that Ruedenberg has so effectively criticized. and Chris Schaller for reading and commenting on this paper.

Chemical Bonds: A Dialog. Prentice Hall: Englewood Cliffs. Molecular Quantum Mechanics. 4th ed.. Oxford University Press: Oxford. In Localization and Delocalization in Quantum Chemistry. 14. et al. Ruedenberg. W. P. The Netherlands. Chem. R. Physik 1928. 6 THE CHEMICAL EDUCATOR ISSN 1430-4171 http://journals. Reidel: Dordrecht. I. Theor. 1991. 1975. Mulliken. Eds.. Harcourt.com/chedr © 1997 SPRINGER-VERLAG NEW YORK. 7.. 1986. INC. N.springer-ny. 3rd ed. 660–664. 43. Chem. Acta 1994. Phys. NO. Levine. 5. W. M. Chapter 1. Phys. G. 2nd ed. 65. Levine. 581–584. 13. Chem. 1997. I. Friedman. R. E. Finkelstein. I. 4th ed. 11. Educ. S2. P. Melrose. M. N. J. NJ. 311–324. Prentice Hall: Englewood Cliffs. 6. 4.K. p 244.. Quantum Chemistry. 9. 16.. U. Kahn. 1988.. Chauhan. R. 4th ed. Adv. pp 73–74. 48. 1970. D. 63. Ruedenberg.. 27–98.. Horowitz.14 / VOL. 15. Oxford University Press: Oxford. p 360. Mehler. Quantum Chemistry. Atkins. E. J. 660–661. Chim. S. B. Levine. 8.. N. U. 1991. pp 362– 363. S.. Am. Quantum Chem. I.. Wiley: Chichester. 1965. J. S 1430-4171 (97)06153-2 3. Baird. J. 10. K. Quantum Chemistry. . Prentice Hall: Englewood Cliffs. NJ. p 355. K. Chalvet O. J. NJ. Nordholm. N. Z. Burdett. 56. P. 1997. 1991. Educ. K. L. M. C. J. 88. Quanta. Vol...K.. 1991. Atkins. Feinberg. S. 118–122. 5. 2. N. F.. 12. 1988. pp 223–245.

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