We have evaluated the performance of various density functionals, covering generalized gradient approximation (GGA), global hybrid (GH) and range-separated hybrid (RSH), using time dependent density functional theory (TDDFT) for computing vertical excitation energies against experimental absorption maximum (λ max ) for a set of 10 different core-substituted naphthalene diimides (cNDI) recorded in dichloromethane. The computed excitation in case of GH PBE0 is most accurate while the trend is most systematic with RSH LCY-BLYP compared to λ max . We highlight the importance of including solvent effects for optimal agreement with the λ max . Increasing the basis set size from TZ2P to QZ4P has a negligible influence on the computed excitation energies. Notably, RSH CAMY-B3LYP gave the least error for chargetransfer excitation. The poorest agreement with λ max is obtained with semi-local GGA functionals. Use of the optimally-tuned RSH LCY-BLYP* is not recommended because of the high computational cost and marginal improvement in results. K E Y W O R D S charge-transfer excitations, density functional calculations, naphthalene diimides, solvent effects, time-dependent density functional theory

Abstract:Despite widespread bench-terracing, stream sediment yields from agricultural hillsides in upland West Java remain high. We studied the causes of this lack of effect by combining measurements at different spatial scales using an erosion process model. Event runoff and sediment yield from two 4-ha terraced hillside subcatchments were measured and field surveys of land use, bench-terrace geometry and storage of sediment in the drainage network were conducted for two consecutive years. Runoff was 3Ð0-3Ð9% of rainfall and sediment yield was 11-30 t ha 1 yr 1 for different years, subcatchments and calculation techniques. Sediment storage changes in the subcatchment drainage network were less than 2 t ha 1 , whereas an additional 0Ð3-1Ð5 t ha 1 was stored in the gully between the subcatchment flumes and the main stream. This suggests mean annual sediment delivery ratios of 86-125%, or 80-104% if this additional storage is included. The Terrace Erosion and Sediment Transport (TEST) model developed and validated for the studied environment was parameterized using erosion plot studies, land use surveys and digital terrain analysis to simulate runoff and sediment generation on the terraced hillsides. This resulted in over-estimates of runoff and under-estimates of runoff sediment concentration. Relatively poor model performance was attributed to sample bias in the six erosion plots used for model calibration and unaccounted covariance between important terrain attributes such as slope, infiltration capacity, soil conservation works and vegetation cover.