Analysis methods are provided that include generating a sample data set using a sample, the sample data set comprising first and second data sets, wherein each of the first and second data sets comprises at least one of an analytical parameter and a sample characteristic acquired using the analytical parameter; and using the first and the second data sets, identifying the sample. Instruments including an ionization source configured to apply different ionization energies to a sample to provide different sample characteristics, and processing circuitry configured to process the different sample characteristics to identify the sample are provided.