Wave Function–Based Quantum Chemistry
7. CONCLUDING REMARKS
In this chapter, we have discussed the rigorous calculation of molecular electronic structure by means of n-electron wave functions. At present, such methods are capable of treating fairly large systems, including systems of biological and pharma-ceutical interest, in an approximate but nonempirical manner, yielding results of qualitative accuracy. Because of their nonempirical nature, such calculations repre-sent a useful, independent source of information about chemical systems, comple-mentary to that obtained by experiment. For high accuracy, hierarchies of methods have been developed, allowing the exact solution to be approached in a systematic manner. At the highest level, wave function-based quantum chemistry provides very accurate information about molecular systems, rivaling that of many experimental measurements.
Although the most accurate calculations are usually not possible on systems of biological interest, a careful calibration of each level in the hierarchy ensures that even the results of the simpler calculations may be used with confidence. Indeed, the presence of such systematic, universally adopted hierarchies is probably the most distinctive feature of modern wave function-based quantum chemistry, setting it apart from other computational techniques of electronic structure.
Figure 7 Normal distributions of the error in calculated reaction enthalpies (kJ/mol).
ACKNOWLEDGMENTS
We thank Dr. M. Schu¨tz (Stuttgart) for permission to reproduce Fig. 4. The research of W. K. is supported by the DFG Research Center for Functional Nanostructures (CFN) under project number C2.3. T. H. gratefully acknowledges support by MOLPROP. P. J. and J. O. acknowledge the support from the Danish National Research Council (grant no. 9901973).
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