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Using a Spreadsheet To Solve the Schrödinger Equations for the Energies of

the Ground Electronic State and the Two Lowest Excited States of H2

Article in Journal of Chemical Education · May 2014

DOI: 10.1021/ed400693p

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Article

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Using a Spreadsheet To Solve the Schrödinger Equations for the

Energies of the Ground Electronic State and the Two Lowest Excited
States of H2
Yingbin Ge,* Robert C. Rittenhouse, Jacob C. Buchanan, and Benjamin Livingston†
Department of Chemistry, Central Washington University, Ellensburg, Washington 98926, United States
*
S Supporting Information

ABSTRACT: We have designed an exercise suitable for a lab or project in an

undergraduate physical chemistry course that creates a Microsoft Excel spreadsheet to
calculate the energy of the S0 ground electronic state and the S1 and T1 excited states of H2.
The spreadsheet calculations circumvent the construction and diagonalization of the Fock
matrix and thus can be accomplished by any undergraduate chemistry student with basic
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calculus skills. The wave functions of the S0, S1, and T1 states of H2 are constructed from the
Publication Date (Web): May 1, 2014 | doi: 10.1021/ed400693p

symmetry-adapted bonding and antibonding molecular orbitals (MO). All quantum

mechanical integrals are estimated using the Monte Carlo integration method. Due to the
stochastic nature of the spreadsheet calculations, 25 runs were carried out to obtain the
mean energy of the S0, S1, and T1 electronic states of H2. The accuracy of the spreadsheet
calculations is comparable to that of the HF/STO-3G calculations. The atomic and
molecular orbitals and the energy components can be easily calculated and plotted for better visualization and understanding of
essential quantum chemical concepts. This spreadsheet can also be adapted to tackle a wider range of quantum chemistry
problems with different levels of complexity.
KEYWORDS: Upper-Division Undergraduate, Physical Chemistry, Computer-Based Learning, Quantum Chemistry,
Computational Chemistry, MO theory

Q uantum chemistry is arguably the most daunting class

for undergraduate chemistry students because it is
highly mathematical and intangible. Efforts have been made to
Halpern and Glendening’s paper,3 we designed a spreadsheet-
aided exercise for students with very basic calculus skills to
estimate the total energy and energy components of the ground
unveil details of self-consistent field (SCF) calculations for and excited states of H2. Matrix construction and operations in
educational purposes: Szabo and Ostlund wrote a FORTRAN the SCF procedures are circumvented by constructing
program to carry out the HF/STO-3G calculation for HeH+ to reasonably accurate total wave functions without optimization.
illustrate the SCF procedures.1 In their FORTRAN program, Integral calculations are simplified by using the Monte Carlo
the following Roothaan−Hall equation is solved iteratively: integration method5,6 to estimate the quantum mechanical
FC = SCε (1) integrals. The optimization of the screening parameter is also
skipped for simplicity. This hands-on exercise provides an
where F is the Fock matrix, C the molecular orbital (MO)
alternative (and very simple) approach to tackle quantum
coefficient matrix, S the overlap matrix, and ε the diagonal
matrix of the MO energies.1 The preceding SCF algorithm was chemistry problems and allows students to focus more on
implemented on an Excel spreadsheet by Page et al., also for quantum mechanical postulates and several important concepts
educational purposes.2 Halpern and Glendening recently without being distracted by too much mathematical detail.
developed a spreadsheet to explore the nature of the H2
bond by using the valence bond (VB), molecular orbital
(MO), and molecular orbital−configuration interaction (MO-
■ THEORY
One of the quantum mechanical postulates states that the
CI) methods;3,4 the authors suggest that students derive and expectation value of the energy of a quantum system can be
then evaluate the analytical expressions of the kinetic energy
calculated given its real wave function ψ using the following
and potential energy terms on a spreadsheet using the provided
expressions of the seven fundamental integrals. However, a equation:
small chemistry program such as the one at the authors’
institution often lacks resources to cover both advanced ∫ ψĤ ψ dτ
E =
calculus and linear algebra in depth. To circumvent the ∫ ψ 2 dτ (2)
construction and diagonalization of the Fock matrix as
described in the Page et al. paper2 and the derivation of the
analytical expressions of the energy components as described in Published: May 1, 2014
© 2014 American Chemical Society and
Division of Chemical Education, Inc. 853 dx.doi.org/10.1021/ed400693p | J. Chem. Educ. 2014, 91, 853−859
 Journal of Chemical Education Article

where Ĥ is the Hamiltonian operator. When the exact wave where xk, yk, and zk are Cartesian coordinates of the kth
function is unavailable, the variational theorem can be used to randomly sampled position of the electron within a box of a
obtain the approximate wave function and energy through the given volume V. The approximation is reasonable if (a) the
minimization of ⟨E⟩. Herein, we introduce a hands-on exercise integrand is a fast decaying function, (b) the volume V is large
that allows students with basic calculus knowledge to solve eq 2 enough that the value of the integrand outside the volume is
approximately for the ground and excited electronic states of negligible, and (c) the number of sampled points Nsampling per
H2 on a spreadsheet. For simplicity, the variational theorem is volume (Nsampling/V) is reasonably large (this poses a practical
not used to optimize the total wave function in the spreadsheet limit to the volume). Two-electron integrals can be calculated
calculations. The molecular orbitals (MO) of H2 are simply in a similar fashion. For example, the expectation value of the
constructed through the linear combination of the exact repulsion between two electrons can be calculated using the
exponential wave function of H atoms; the total wave function following equation:
is then constructed from the MOs.
In the description of this exercise and in all spreadsheet 1 ∫ ψ r112 ψ dτ
calculations, four fundamental atomic units (au) are used for =
simplicity and clarity:
r12 ∫ ψ 2 dτ
⎛ Nsampling k 2
me = 1 au (3) ⎜ ∑k = 1 (ψ )
≈⎜
( ) V ⎞⎟⎟/⎛⎜ ∑
1
r12 k 2
Nsampling
k=1
(ψ k)2 ⎞
V 2⎟⎟
e = 1 au (4) ⎜
⎜⎜ Nsampling ⎟⎟ ⎝ Nsampling ⎠
h ⎝ ⎠
ℏ= = 1 au
2π (5) N
(ψ k)2 ( )
1
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∑k =sampling
1 r12 k
1 =
Publication Date (Web): May 1, 2014 | doi: 10.1021/ed400693p

= 1 au N
∑i =sampling (ψ k)2
4πε0 (6) 1 (11)

where me is the mass of an electron, e the charge of a proton, h where ψ = ψ (x1, y1, z1, x2, y2, z2) and dτ = dx1 dy1 dz1 dy2 dz2.
the Planck constant, ℏ the reduced Planck constant, and ε0 the The volume appearing in the preceding equation is squared
dielectric constant in vacuum. The atomic units for length and both in the numerator and denominator because the integrands
energy can be derived from the above four fundamental atomic are functions of the x/y/z coordinates of two electrons. The ψk
units: and r12k are the numerical values of ψ and r12 at the kth
randomly sampled positions of the two electrons. Note that the
(4πε0)ℏ2 numerator in the last term of the above equation is simply the
1 au of length =
mee 2 (7) weighted sum of the repulsion between the two electrons,
where the weight, (ψk)2, is the probability density of finding the
mee 4 two electrons at their corresponding positions.
1 au of energy = In the spreadsheet calculations, the total wave function ψ is
(4πε0)2 ℏ2 (8)
constructed from MOs that are linear combinations of real
The total energy of H2 consists of the nucleus−nucleus (N− exponential functions (e−r). Note that e−r is the exact solution
N) repulsion energy and the electronic energy. The N−N to the H atom, where r is in the atomic unit of length (1 au =
repulsion in H2 equals 1/RAB, where RAB is the distance 0.529177 Å). The following antisymmetric wave functions are
between the two H nuclei A and B. The electronic energy Eelec used for the H2 singlet ground state (S0), the first excited
of H2 is calculated using the following equation: singlet state (S1), and the first triplet excited state (T1) with a
magnetic quantum number of zero:7
∫ ψ Helecψ̂ dτ
Eelec =
∫ ψ 2 dτ ψ (S0) = [σ(1) σ(2)][α(1) β(2) − α(2) β(1)] (12)
⎡ ⎤
( −21 ∇12 + −21 ∇22 ) + ( r−1 + r−1 + r−1 + r−1 ) + ( r1 )
∫ ψ ⎢⎣ 1A 1B 2A 2B 12
⎥⎦ψ dτ ψ (S1) = [σ(1) σ *(2) + σ(2) σ *(1)][α(1) β(2) − α(2) β(1)]
= (13)
∫ ψ 2 dτ
(9) ψ (T)
1 = [σ (1) σ *(2) − σ (2) σ *(1)][α(1) β(2) + α(2) β(1)]
(14)
The terms enclosed within the first, second, and third
parentheses are the quantum mechanical operators of kinetic where σ and σ* denote the unnormalized symmetry-adapted
energy, attraction, and repulsion of electrons, respectively. The bonding and antibonding orbitals:
analytical expressions of the integrals appearing in eq 9 are very σ(i) = ΦiA + ΦiB = e−riA + e−riB (15)
complex when either exponential functions3 or Gaussian-type
functions2 are used to construct the total wave function ψ. σ*(i) = ΦiA − ΦiB = e−riA − e−riB (16)
Therefore, we estimate all quantum mechanical integrals using
the Monte Carlo integration method,5,6 a technique especially where i = 1, 2 denotes the coordinates of the ith electron in H2,
useful for high-dimensional integration. For example, the ΦiA = e−riA is the atomic function of nucleus A, and ΦiB = e−riB is
integral of a function f of the xyz coordinates of an electron the atomic function of nucleus B. The α and β spin functions
can be estimated as follows: are orthonormalized.
+∞ N
In eqs 12−14, the spin part of the total wave function is
∑k =sampling f (x k , y k , z k ) separated from the spatial part and thus the spin integrals can
∭ f (x , y , z ) d x d y d z ≈ 1
Nsampling
V be separated and canceled in eq 2 because the Hamiltonian
−∞ (10) operator does not contain spin coordinates. Therefore, the spin
854 dx.doi.org/10.1021/ed400693p | J. Chem. Educ. 2014, 91, 853−859
 Journal of Chemical Education Article

functions in eqs 12−14 can be neglected, and the following −1 2 −1 ⎡ ∂ ⎛ 2 ∂ ⎞⎤ −riX ⎛ 1 1⎞

spatial functions are used to describe the first three electronic ∇i ΦiX = ⎢
2⎢ ⎜riX ⎟⎥e = ⎜ − ⎟e−riX
states of H2 in the spreadsheet calculations: 2 2riX ⎣ ∂riX ⎝ ∂riX ⎠⎦⎥ ⎝ riX 2⎠
(24)
ψ (S0) = σ(1) σ(2) (17) where i = 1, 2 and X = A, B. Therefore, eqs 21−24 can be used
to calculate the numerical value of ψ(T1)[(−1/2)∇12 + (−1/
ψ (S1) = σ(1) σ *(2) + σ(2) σ *(1) (18) 2)∇22]ψ(T1) at each randomly sampled point within the
integral limits. The expectation value of the total kinetic energy
ψ (T) of the two electrons can then be estimated using eq 20. The
1 = σ (1) σ *(2) − σ (2) σ *(1) (19)
kinetic energy of the electrons in the S0 and S1 states can be
The spreadsheet calculations of the integrals of the electron obtained in a similar fashion.
density, attraction, and repulsion require no more than Once the kinetic energy, N−e attraction, e−e repulsion, and
algebraic skills. Students may derive and simplify the analytical N−N repulsion are calculated on the spreadsheet, the total
expression of the expectation value of the repulsion in the T1 energy can be easily obtained. We recommend repeating the
electronic state and should understand that the negative above calculations multiple times to obtain the mean values of
exchange energy originates from the negative cross-terms the energy components and the total energy because of the
(−2∫ σ(1) σ*(1) σ(2) σ*(2)/r12 dτ) that appear in the stochastic nature of the Monte Carlo integration method being
used to estimate the integrals.

■
numerator. Numerical values of these cross-terms and the
corresponding exchange energy can be estimated by slightly
modifying the spreadsheet. Motivated students may resort to RESULTS AND DISCUSSION OF SAMPLE
CALCULATIONS
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more advanced quantum chemistry textbooks such as Szabo

and Ostlund’s Modern Quantum Chemistry to better understand
Publication Date (Web): May 1, 2014 | doi: 10.1021/ed400693p

Due to the stochastic nature of the integral calculations through

exchange (and even correlation).8 random sampling of the values of the integrand, we carried out
The kinetic energy integral calculations require a simple a total of 25 runs on a spreadsheet for the H2 molecule with a
derivation that employs basic differential calculus. Taking the fixed bond distance of 1.5 au. Each run contains 40,000
T1 electronic state for example, the expectation value of the randomly sampled data points within the x/y/z integral limits
kinetic energy of the two electrons can be calculated using the of 6/6/7.5 as the H2 molecule is placed along the z axis
following equation: illustrated in Figure 1.
−1 2 −1 2
1 ( 2 ∇1 +
∫ ψ (T) 2 2
∇ )ψ (T)1 dτ
KE = 2
∫ [ψ (T)]
1 dτ
⎡ψ (T )
N
∑i =sampling
1 ⎣ 1 ( −21 ∇12 + −21 ∇22 )ψ (T)1 ⎤⎦
≈ N
∑i =sampling
1
[ψ (T1)]2 (20)

where ψ(T1) = σ(1) σ*(2) − σ(2) σ*(1). The numerator

includes the kinetic energy terms of electrons 1 and 2 that can
be evaluated numerically on the spreadsheet after the following
derivations:
⎛ −1 2 −1 2 ⎞⎟
⎜ ∇ + ∇2 ψ (T)
⎝ 2 1 2 ⎠ 1
−1 2
= ∇1 [σ(1) σ *(2) − σ(2) σ *(1)]
2 Figure 1. H2 with a bond length of 1.5 au placed in a 6 × 6 × 7.5 box.
−1 2 The dimensions of the box, also in au, illustrate the limits of the
+ ∇2 [σ(1) σ *(2) − σ(2) σ *(1)] integrals calculated on the spreadsheet.
2
⎡ −1 2 ⎤ ⎡ −1 2 ⎤
= σ *(2)⎢ ∇ σ(1)⎥ − σ(2)⎢ ∇ σ *(1)⎥ Note that the boundary of the box is at least 3 au away from
⎣ 2 1 ⎦ ⎣ 2 1 ⎦ the H nuclei. This distance of 3 au is chosen because the
⎡ −1 2 ⎤ ⎡ −1 2 ⎤ probability of finding the electron inside the sphere with a
+ σ(1)⎢ ∇2 σ *(2)⎥ − σ *(1)⎢ ∇2 σ(2)⎥ radius of 3 au is ∼94% in a hydrogen atom. Therefore, we may
⎣ 2 ⎦ ⎣ 2 ⎦ (21)
assume that the electron probability density of the H2 molecule
Given σ(i) = ΦiA + ΦiB and σ*(i) = ΦiA − ΦiB, we have is very small outside the 6 × 6 × 7.5 box. Meanwhile, the
volume is still small enough that as many as 148 data points are
−1 2 −1 2 −1 2 sampled per atomic unit of volume (equivalent to ∼1000 data/
∇i σ(i) = ∇i ΦiA + ∇i ΦiB
2 2 2 (22) Å3); this helps reduce the error introduced by the discrete
approximation of integrals. The atomic orbitals and the
−1 2 −1 2 −1 2 bonding and antibonding molecular orbitals are presented in
∇i σ *(i) = ∇i ΦiA − ∇i ΦiB Figure 2 by plotting the numerical values of e−r1A, e−r1B, and e−r1A
2 2 2 (23)
± e−r1B versus the z coordinates of electron 1. Note that these
And it can be easily proven that atomic and molecular wave functions may adopt different
855 dx.doi.org/10.1021/ed400693p | J. Chem. Educ. 2014, 91, 853−859
 Journal of Chemical Education Article

HF/cc-pV6Z energies) is −1.131387 au using the E = A + B(L

+ 1)−4 equation11 or −1.131371 au using the E = A + Be−9√L
equation,12 where L is the number of the s-type functions. The
HF/cc-pV6Z energy (−1.131368 au) agrees with these two
extrapolated HF limits within 10−4 au of energy. Therefore, the
HF/cc-pV6Z calculations are used as the benchmark hereafter.
Figure 3 shows the spreadsheet calculations are more
accurate than the HF/STO-1G calculations and are comparable
to the HF/STO-2G and HF/STO-3G calculations. The
spreadsheet predictions are in better agreement with the HF/
cc-pV6Z benchmark at stretched bond lengths because the
exponential wave functions are the exact wave functions at the
dissociation limit. It is worth noting that neither the HF PES
curves nor the spreadsheet-calculated energies describe the
dissociation limit properly. This is because in the HF
Figure 2. Plots of 5000 randomly sampled numerical values of the calculations of the S0 state of H2 at the dissociation limit, the
atomic orbitals: (A) e−r1A and (B) e−r1B and the molecular orbitals: (C) two electrons are forced to occupy the same spatial molecular
e−r1A + e−r1B, and (D) e−r1A − e−r1B. orbitals (known as the restricted Hartree−Fock or RHF
theory) while they are supposed to occupy two different
numerical values at a fixed value of z because x and y orbitals each centered on a different nucleus. A proper
coordinates are randomly sampled. description at stretched bond distances can be obtained by
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The plots of the atomic orbitals are not exactly symmetrical breaking the symmetry of the molecular orbitals using open-
Publication Date (Web): May 1, 2014 | doi: 10.1021/ed400693p

because neither nucleus A or B is placed at the center of the z shell wave functions such as in an unrestricted HF (UHF)
axis and also because the sampling of the positions of the calculation.13 To further demonstrate the failure of the RHF
electron is random. The constructive and destructive theory and the success of the UHF theory at the dissociation
interferences between the two atomic orbitals are clearly limit of H2, we used the spreadsheet to calculate the energies of
illustrated in the plots of the bonding and antibonding the S0, S1, and T1 electronic states at the bond distance of 10 au
molecular orbitals. of length. The S0, S1, and T1 energies are determined to be
We have also carried out spreadsheet calculations to obtain −(0.691 ± 0.131), −(0.394 ± 0.227), and −(1.000 ± 0.000)
the single-point energy of the S0 state of H2 at various au, respectively. Our S0 energy is close to the HF energy
internuclear distances ranging from 0.8 to 3.5 au of length. In (−0.6875 au) at infinite bond distance calculated by Halpern
each calculation, the x/y dimensions of the box are set to be 6 and Glendening using the same exponential basis functions.3
au of length; the z dimension is set to be 6 au plus the bond For further comparison, the HF/cc-pV6Z energies of the S0 and
distance. The spreadsheet-calculated average energy and T1 states are −0.768 and −1.000 au at the bond distance of 10
standard deviation are illustrated in Figure 3 in comparison au, while the exact HF energies of the S0 and T1 states are
supposed to be exactly −1 au at the dissociation limit.
Because the relative energyrather than the absolute
energyis of more interest to chemists, binding energy (BE)
is calculated using the BE = |E(H2) − 2E(H)| equation. The
spreadsheet predicts the atomic energy of H to be exactly −0.5
au and the minimum energy of H2 to be −(1.102 ± 0.023) au;
thus the binding energy of H2 in the ground state is determined
to be 0.102 ± 0.023 au excluding the zero-point vibrational
energy (ZPVE) correction. Our result is very close to Halpern
and Glendening’s HF binding energy of 0.099 au using the
same basis set but calculated in an analytical and deterministic
manner.3 For comparison, the HF binding energies are 0.167,
0.185, 0.184, and 0.134 au using the STO-1G, STO-2G, STO-
3G, and cc-pV6Z basis sets, respectively. Among the above HF
energies, the HF/STO-1G energy is the closest to the
experimental binding energy at 0 K (0.17446 au without the
Figure 3. Spreadsheet-calculated potential energy surface of H2 in the ZPVE correction14) only because of the fortuitous cancellation
S0 electronic state versus those calculated at the HF level of theory of errors that originate from the very small basis set and from
with the STO-1G, STO-2G, STO-3G, and cc-pV6Z basis sets. the lack of correlation in the molecular calculation. The
spreadsheet-calculated binding energy contains the largest error
with the HF/STO-1G, HF/STO-2G, and HF/STO-3G of all partly because the error in the energy calculation for the
potential energy surfaces (PES). The HF/cc-pV6Z PES is H2 molecule cannot be canceled by any error in the calculation
also plotted serving as the benchmark within the realm of HF for the H atom.
theory. All of the HF calculations were carried out using the The spreadsheet-calculated PES reaches the minimum at the
GAMESS package.9,10 Note that the cc-pV6Z basis set bond distance of ∼1.5 au of length. This bond distance is
(6s5p4d3f on H) is large enough to provide a close estimate reasonably close to the experimental bond distance of H2
of the HF limit. For example, at the 1.5 au bond distance, the (1.401 au or 0.7414 Å)14 at equilibrium. It is also reasonably
HF limit (two-point extrapolation from the HF/cc-pV5Z and close to the equilibrium bond distance (1.603 au) calculated by
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 Journal of Chemical Education Article
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Publication Date (Web): May 1, 2014 | doi: 10.1021/ed400693p

Figure 4. Spreadsheet versus HF/STO-3G calculated results for H2 at the bond distance of 1.5 au: (A) total energy, (B) attraction, (C) e−e
repulsion, (D) potential energy, and (E) kinetic energy. The HF/cc-pV6Z data are plotted serving as the benchmark.

Figure 5. The mean (A) and the standard deviation (B) of the total energy of the S0, S1, and T1 electronic states of H2 with various numbers of
sampled data (Nsampling = 2,500, 5,000, 10,000, 20,000, 40,000).

Halpern and Glendening using the same exponential basis calculations are slightly less accurate than the HF/STO-3G
functions in their MO calculations.3 Therefore, we made more calculations for the ground state and are notably more accurate
detailed comparison of energy components at this bond for the excited states; similar patterns of the ranking of accuracy
distance between the spreadsheet calculations and the HF/ are observed for each energy component illustrated in Figure
STO-3G calculations in Figure 4. The HF/cc-pV6Z data are 4B−E.
also plotted serving as the benchmark. At the bond distance of 1.5 au, we also varied the value of
At the bond distance of 1.5 au, the average and standard Nsampling to 20,000, 10,000, 5,000, and 2,500 to test the
deviation of the 25 spreadsheet calculations of the total energy robustness of the spreadsheet calculations using fewer sampled
of the S0, S1, and T1 electronic states were −(1.102 ± 0.023), data. Figure 5A shows that the mean values of the 25 runs are
−(0.410 ± 0.035), and −(0.682 ± 0.018) in atomic units. The statistically the same regardless of the Nsampling value used within
energies of the S0, S1, and T1 electronic states are −1.112, the wide range from 2,500 to 40,000. Figure 5B shows that the
−0.222, and −0.591 au at the HF/STO-3G level of theory and standard deviation of the total energy is found to be
are −1.131, −0.674, and −0.794 au at the HF/cc-pV6Z level of asymptotically inversely proportional to the square root of
theory. Although only one basis function is employed on each the number of the sampled data per volume. Therefore, if the
H atom in the spreadsheet calculations, the quality of the PES is of interest, we suggest using a sample size of 40,000 (or
results is satisfactory: Figure 4A shows the spreadsheet even more) data in each run to achieve a reasonable precision.
857 dx.doi.org/10.1021/ed400693p | J. Chem. Educ. 2014, 91, 853−859
 Journal of Chemical Education

■
Article

Even when a very large number of data are sampled, the ASSOCIATED CONTENT
computing time is not likely an issue because it takes only a *
S Supporting Information
split second to perform one run with 40,000 sampled data on a
Windows PC with one CPU of 3.20 GHz frequency and the Text describing a sample exercise including the step-by-step
computing time scales linearly with Nsampling. instruction of the construction of the spreadsheet and the

■
procedures of calculations and tables listing a Microsoft Excel
spreadsheet that contains the sample calculations of the S0, S1,
ADDITIONAL EXERCISES T1 electronic states of H2 and graphs and a much smaller
Although this spreadsheet is designed to calculate the Hartree− EXCEL spreadsheet that contains only a template with 2500
Fock energies of the S0, S1, and T1 electronic states of H2, sampled data. This material is available via the Internet at
quantum chemistry instructors may also develop many other http://pubs.acs.org.
activities appropriate for students at different levels. For
example, this spreadsheet can be easily modified to calculate
the energies of one-electron systems such as the H atom and
■ AUTHOR INFORMATION
Corresponding Author
the H2+ molecule. Students may also estimate the energy of the
*E-mail: yingbin@cwu.edu.
first excited state using a Hartree product wave function, σ(1)
σ*(2), which corresponds to the average of the S1 state shown Present Address
†
in eq 13 and the T1 state with a zero magnetic quantum Department of Mathematics, Oregon State University,
number shown in eq 14; they will be able to compare the Corvallis, OR 97331, United States.
Hartree-product wave function with the properly constructed Notes
wave functions for the S1 and T1 states. In this proposed
The authors declare no competing financial interest.
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■
spreadsheet calculations, the exponential coefficients in the
atomic functions are fixed. The optimization of the exponential
Publication Date (Web): May 1, 2014 | doi: 10.1021/ed400693p

coefficients may further lower the energy of the S0 state as ACKNOWLEDGMENTS

shown in Halpern and Glendening’s paper3 although a much Y.G. is thankful for the Faculty Summer Grant provided by the
larger sampling is required to achieve the desired accuracy in College of the Sciences of Central Washington University.
the stochastic spreadsheet calculations. Mathematically ad-
vanced students may calculate the energies of higher lying
excited states of H2 and H2+ using properly constructed wave
■ REFERENCES
(1) Szabo, A.; Ostlund, N. S. Modern Quantum Chemistry, 1st ed.;
functions. Because the proposed method and the density McGraw-Hill: New York, 1982; pp 410−436.
functional theory (DFT) method are similar in calculating (2) Page, T. R.; Boots, C. A.; Freitag, M. A. Quantum Chemistry:
discrete quantities weighted by electron probability density, Restricted Hartree-Fock SCF Calculations Using Microsoft Excel. J.
students may modify the spreadsheet to conduct simple DFT Chem. Educ. 2008, 85, 159.
calculations within the local density approximation (For exam- (3) Halpern, A. M.; Glendening, E. D. Exploring the Nature of the
H2 Bond. 1. Using Spreadsheet Calculations To Examine the Valence
ple, by using the VWN exchange-correlation equation15).
Bond and Molecular Orbital Methods. J. Chem. Educ. 2013, 90, 1452−
Students with some programming experience and strong 1458.
interest in computational chemistry may even implement the (4) Halpern, A. M.; Glendening, E. D. Exploring the Nature of the
algorithm using FORTRAN or any other programming H2 Bond. 2. Using ab Initio Molecular Orbital Calculations To Obtain
language they are comfortable with. The wide range of activities the Molecular Constants. J. Chem. Educ. 2013, 90, 1459−1462.
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859 dx.doi.org/10.1021/ed400693p | J. Chem. Educ. 2014, 91, 853−859

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