Semi-Empirical Methods

In the Hartree-Fock (HF) methods, the largest cost is associated with computing and handling the many twoelectron integrals (M4). Many of the two-electron integrals are very small. Semi-empirical methods neglect many of these small integrals and are thus much less computationally demanding. Other approximations common to semi-empirical methods:
Only include valence orbitals explicitly Use a minimum basis set, i. e. one function for each atomic valence orbital Use Slater type basis function (exponentials)
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Zero Differential Overlap (ZDO)

In any integral, a term involving the product of basis functions on two different centers is taken to be zero.

A (ri ) B (ri ) 0 where A B

Consequences of the zero differential overlap assumption:
The overlap matrix becomes the unit matrix, Sij = ij One-electron integral involving three centers are set to zero. All three and four-center two electron integrals are set to zero.

ZB C 0, r RB

A B C B 0, and

A B C D 0

Empirical Corrections
To compensate for the neglected integrals, the remaining integrals are made into parameters and adjusted to give results that agree with either atomic or molecular experimental data. Note that a different set of Greek letters are traditionally used in discussing the semi-empirical methods. The Fock matrix thus has the form:

Neglect of Diatomic Differential Overlap Approximation (NDDO)

Essentially this is just the ZDO approximation. S = A B = AB Overlap: One-electron integrals (Za is the nuclear charge on center a reduced by the number of core electrons) 1 Za 1 h = 2 = 2 Va 2 2 Ra r a a 1 A h A = A 2 VA A A Va A 2 a A 1 A h B = A 2 VA VB B 2
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F = h + D [
,

AO

h = h

where

A VC B 0
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Additional Integral Approximations in NDDO

The one-center one-electron integrals are assumed to form a diagonal matrix. This would be exactly true only if the basis functions were eigenfunctions of the one-electron Hamiltonian for that center. 1 1 A 2 VA A = A 2 VA A 2 2 The two electron integrals are assumed to satisfy:

Intermediate Neglect of Differential Overlap Approximation (INDO)

All approximations made in the NDDO method Two-center two-electron integrals that are not of the Coulomb type are neglected. In order to maintain rotational invariance, some integrals are made to be independent of the orbital type (i. e. an integral involving a p function must have the same value as the corresponding integral involving the s function on the same center.

A B C D = ACBD A B A B
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Form of Integrals in INDO

The invariance property yields the following:

Complete Neglect of Differential Overlap (CNDO)

A h A A Va A

1 = A 2 A A Va A 2 a

All approximations made in the INDO method One-center two-electron integrals that are not of the Coulomb type are neglected.

is independent of orbital type (s or p )

A B C D = AC B D A B A B A B A B is independent of orbital type

Thus there are only two two-electron integrals:

Two-electron two-center integrals have the form:

A B C D = AC B D A B A B
where A B and A B A B is independent of orbital type

A A A A = A A A A = AA A B A B = AB AB = AB
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Limitations of the Semi-Empirical Methods

The form of these semi-empirical methods is the same as the HF method. With the minimum basis sets used in the semi-empirical methods, the HF method only gives a qualitative picture. Thus, to allow the semi-empirical methods to be useful, the integrals retained in these methods are parameterized to correct for:
The limitations of the HF method The limitations of the minimum basis set The limitations of the ZDO approximations

Parameterization of the Semi-Empirical Methods

There are three basic approaches to parameterize the integrals that are retained in the semi-empirical methods: 1. The integrals can be calculated from the functional form of the atomic orbitals. 2. The integrals can be made into parameters, which are assigned values based on a few (usually atomic) experimental data. 3. The integrals can be made into parameters, which are assigned values based on fitting many (usually molecular) experimental data.
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Modified Intermediate Neglect of Differential Overlap (MINDO)

MINDO is based on the INDO approach, where only Coulomb type two-center integrals are retained. The term Modified in this case refers to the fact that the integrals are parameterized use experimental molecular data. MINDO/3, developed in 1975 by Dewars group, was the first useful semi-empirical method. In MINDO/3 the two electron integrals were parameterized for each pair of atoms. Parameters are for H, B, C, N, O, F, Si, P, S, Cl. Parameterized to obtain fit of heats of formation, geometries, and dipole moments.

Modified NDDO Methods

Several successful methods are based on parameterizations of the NDDO method. These methods include:
MNDO, Modified Neglect of Differential Overlap AM1, Austin Model 1 PM3, Parametric Method 3 (MNDO being 1 and AM1 being 2)

One-center two-electron integrals are parameterized to obtain accurate atomic ionization energies. Two-center two-electron integrals are written as functions of the one-center two electron integrals and the exponents of the basis functions.
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Modified Neglect of Diatomic Overlap (MNDO)

The main difference between the various modified NDDO methods is the form of the core-core interaction (Vnn).
MNDO sA sB sA sB 1 + e A RAB + eBRAB ZB Vnn ( A,B) = Z A

Austin Model 1 (AM1)

The AM1 model is essentially the same as the MNDO model except that additional terms have been added to the core-core interaction to make it less strongly repulsive at intermediate distances (2-3 ).
AM1 MNDO Vnn ( A,B) = Vnn ( A,B) +

The interactions involving OH and NH bonds are treated differently. e A RAH R MNDO Vnn A,H = Z Z s s s s + e H AH ( ) A H A H A H 1 + RAH For some lighter elements s = p
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ZB ZA RAB

bkA ( RAB ckA )2 bkB ( RAB ckB )2 a e + a e kB kA k k Where the sums over k have 2 to 4 terms depending on the atom.
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Parametric Method 3 (PM3)

This method has the same functional form as the AM1 method. The parameters are obtained from a global optimization over a set of molecules rather than using the atomic data to determine the values of the one-center two-electron integrals. Only two terms (k = 1 and 2) are used for all atoms in the core-core interaction terms. PM3 has been parameterized for a number of atoms: H, Li, C, N, O, F, Mg, Al, Si, P, S, Cl, Zn, Ga, Ge, As, Se, Br, Cd, In, Sn, Sb, Te, I, Hg, Rl, Pb, Bi, Po, and At.
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Common Limitations of the MNDO, AM1, and PM3

Rotational barriers for bonds which have partly double bond character are significantly too low, e. g. the barrier to rotation about the central bond of butadiene is found to be 0.5-2.0 kcal/mol rather than the experimental value of 5.9 kcal/mol. Weak interactions such as van der Waals complexes or hydrogen atoms are poorly predicted, yielding interactions that are too weak or the wrong geometries. The bond length of nitrosyl groups are underestimated, e. g. the N-N bond in N2O3 is 0.7 too short. Results for molecules includes metals are not reliable.
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MNDO/d Method
The MNDO/AM1/PM3 methods only include s and p functions. It is known that d atomic orbitals are inportant in describing the bonding in the second row atoms. This is particularly true for hyprevalent species. Then MNDO/d method has been parameterized to include the d orbitals for Na, Mg, Al, Si, P, S, Cl, Br, I, Zn, Cd, and Hg.

Performance of Semi-Empirical Methods

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Performance of Semi-Empirical Methods

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