Experimental and theoretical examples of the value and limitations of transition state theory

Value and limitations of transition-state theory (TST) are reviewed. TST analyses of the temperature dependence of the ''direct'' reactions CH/sub 3/ + CH/sub 3/CHO ..-->.. CH/sub 4/ + CH/sub 3/CO (1) and O + CH/sub 4/ ..-->.. OH + CH/sub 3/ (2) are presented in detail, and other examples of TST usefulness are recalled. Limitations are discussed for bimolecular processes in terms of ''complex'' vs ''direct'' mechanisms. The reaction OH + CO ..-->.. CO/sub 2/ + H is discussed in this context. Limitations for unimolecular processes seem to arise only for simple bond fission processes, and recent advances are noted. 2 figures, 5 tables.