Table 7.

Main delocalization energies (in kJ/mol) for three species of S(-)-promethazine in gas and aqueous solution by using B3LYP/6-31G* calculations.

B3LYP/6-31G*a
Delocalization	Free base		Hydrochloride
	Gas	PCM	Gas	PCM
πC6-C13→ π*C9–C15	74.32	74.28	73.40	73.19
πC6-C13→ π*C17–C19	88.41	88.49	85.98	85.77
πC7-C14→ π*C10–C16	74.49	74.61	72.73	72.02
πC7-C14→ π*C18–C20	88.28	88.49	85.23	85.19
πC9-C15→ π*C6–C13	83.56	83.39	85.27	85.27
πC9-C15→ π*C17–C19	71.18	71.27	72.02	71.98
πC10-C16→ π*C7–C14	83.81	83.60	85.90	86.19
πC10-C16→ π*C18–C20	71.52	71.60	72.23	72.10
πC17-C19→ π*C6–C13	79.59	79.59	81.34	81.97
πC17-C19→ π*C9–C15	93.84	93.67	94.09	94.26
πC18-C20→ π*C7–C14	80.05	80.21	82.05	82.26
πC18-C20→ π*C10–C16	93.75	93.67	94.26	94.30
Σπ→π*	982.8	982.87	984.5	984.5
LP(2)S1→ π*C9–C15	45.98	45.44	46.27	46.02
LP(2)S1→ π*C10–C16	45.98	45.23	46.36	46.27
LP(1)N2→ π*C6–C13	99.86	99.36	92.96	94.89
LP(1)N2→ π*C7–C14	100.74	99.44	94.30	97.56
ΣLP→π*	292.56	289.47	279.89	284.74
π*C9–C15→ π*C17–C19	1106.65	1113.09
π*C10–C16→ π*C18–C20	1127.35	1136.79
π*C6–C13→ π*C17–C19			1101.14	978.58
π*C7–C14→ π*C18–C20			909.65	805.44
π*C9–C15→ π*C17–C19			1057.33	1045.67
π*C10–C16→ π*C18–C20			1040.23	1046.42
Σπ*→π*	2234	2249,88	4108,35	3876,11
σN3-C4→ LP(1)*H41			44,60	62,57
σN3-C11→ LP(1)*H41			50,08	62,82
σN3-C12→ LP(1)*H41			47,61	60,19
Σσ→LP*			142,29	185,58
LP(1)N3→ LP(1)*H41			1158,49	1456,02
LP(1)Cl42→ LP(1)*H41			46,94	16,51
LP(4)Cl42→ LP(1)*H41			797,46	306,06
ΣLP→LP*			2002,89	1778,59
ΣTOTAL	3509.36	3522,22	6253,53	5840,28
Cationica
Delocalization	Gas
πC13-C17→ π*C6–C9	47.86
πC15-C19→ π*C6–C9	43.22
πC15-C19→ π*C13–C17	46.98
Σπ→π*	138.06
πC7-C10→ LP(1)*C16	93.51
πC18-C20→ LP(1)*C16	107.22
Σπ→LP*	200.73
LP(1)C14→ π*C7–C10	171.17
LP(1)C14→ π*C18–C20	125.57
LP(1)C16→ π*C7–C10	176.65
LP(1)C16→ π*C18–C20	133.97
ΣLP→π*	607.36
π*C6–C9→ π*C13–C17	361.99
π*C6–C9→ π*C15–C19	232.87
Σπ*→π*	594.86
ΣTOTAL	1541.01

The letters bold indicated RMSD values.

^aThis work.