No, the act does not cover Employees when not on duty.
The scope of the act is to provide for adequate protection to Employees when they suffer any injury or losses caused by an accident during the course of employment. The Employer is therefore not liable when the Employee is not on duty.
The courts in India and abroad have at various times passed judgements that cases like these need to be considered on a case to case basis.
While a routine to and from work need not fall under the Employers liability, occasions where an Employee is commuting primarily for work, like traveling between two offices, would fall under the Employers liability.